Derivatives of N-HALS-substituted amic acid hydrazides

ABSTRACT

N-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acid hydrazides contain a light stabilizing group, a heat stabilizing group and an amic acid hydrazide functionality in the same molecule. The amic acid hydrazide functionality in the compounds enhances the photooxidative stabilizing properties of the hindered amine groups and contributes thermal and oxidative stabilizing and metal complexing properties to the compounds. The novel compounds are excellent light stabilizers for polyolefins, have low volatility and are not readily lost from polymeric systems via volatilization, migration or extraction.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of copending U.S. patentapplication Ser. No. 07/455,219, filed Feb. 22, 1989 now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel derivatives ofN-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acid hydrazides. Thesecompounds are very efficient in the stabilization of polymeric systemswhich are subject to degradation upon exposure to heat and/or light.

Particularly, this invention is related to acyl, carbamoyl,thiocarbamoyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl,cycloalkoxycarbonyl, aliphatic, alicyclic, araliphatic, aryl,2-hydroxyalkyl, 2-hydroxycycloalkyl and hydrazone derivatives ofN-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acid hydrazides.

2. Description of the Prior Art

Derivatives of hindered amine light stabilizing-substituted hydrazides(HALS-substituted hydrazides) are disclosed in U.S. Pat. Nos. 4,145,512and 4,178,279. These patents teach reacting hindered amine lightstabilizers (HALS) containing carboxylic acid hydrazide groups withisocyanate groups of polyisocyanates or isocyanate prepolymers to obtainlight stabilized polyurethanes. However, the HALS-hydrazides employedwere not HALS-substituted amic acid hydrazides and therefore do not havethe enhanced stabilizing effect of the novel derivatives of the presentinvention.

U.S. Pat. No. 4,336,183 discloses various HALS spiro compoundscontaining a hydrazide functionality. It also discloses various acylderivatives of these hydrazides. However, none of the hydrazides areN-HALS-substituted amic acid hydrazides and consequently the derivativesdo not fall under the scope of the present invention.

U.S. Pat. No. 4,983,738, assigned to the assignee of the presentinvention, disclose N-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acidhydrazides from which the compounds of the present invention may beprepared. These compounds are efficient light stabilizers for polymericsystems; however, the disclosed compounds have some volatilitylimitations and can be extracted out of the polymers to some degree bywater or aqueous solutions.

U.S. Pat. No. 4,824,884, assigned to the assignee of the presentinvention, discloses cyclic anhydride derivatives ofN-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acid hydrazides. Thesecompounds are also efficient heat and light stabilizers for polymericsystems but do not fall under the scope of this invention.

Prior to the present invention, the results obtained with the knownhindered amine light stabilizers have not been satisfactory with alltypes of manufactured articles, due to certain deficiencies instabilization, compatibility, volatility, exudability or economics.Therefore, further improvement in the field of hindered amine lightstabilizers is still desirable. The novel compounds of this inventionaddress these shortcomings.

DEFINITIONS

Throughout the disclosure, when referring to"2,2,6,6-tetraalkylpiperidines" or "2,2,6,6-tetraalkyl-4-piperidinylgroups", the piperidinyl groups optionally substituted in the 3 positionof the piperidine group with lower alkyl groups of 1-4 carbons are alsoincluded, i.e., the structure having the formula: ##STR1## where R andR¹ are as defined hereinafter.

The term "acyl" refers to a radical generated from a carboxylic acid bythe removal of the OH group to provide a free valence on the C(═O)group, for example, DC(═O)OH would become the DC(═O) substituentreferred to generally as a D acyl group.

As used herein, the terms "polymer" or "polymeric composition(s)"include homopolymers or any type of copolymers.

Where any symbol appears more than once in a formula, its meaning ineach instance is independent of one another.

SUMMARY OF THE INVENTION

This invention is directed to a derivative ofN-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acid hydrazide having theFormula I: ##STR2## wherein R is hydrogen, oxyl, hydroxy, substituted orunsubstituted aliphatic of 1-20 carbons, substituted or unsubstitutedalicyclic of 5-12 carbons, substituted or unsubstituted araliphatic of7-22 carbons, substituted or unsubstituted aliphatic acyl of 2-20carbons, substituted or unsubstituted alicyclic acyl of 7-16 carbons,substituted or unsubstituted aryl acyl of 7-11 carbons, substituted orunsubstituted araliphatic acyl of 8-22 carbons, --C(═O)N(R⁶)(R⁷),--(C(═O))_(a) O--R⁸, --(CH₂)_(a) C(═O)O--R⁹ or --(CH₂ --CH(R¹)--O)_(b)--R¹⁰ ;

n is 1 or 2;

a is 1 or 2;

b is an integer of 2-50;

R¹ is hydrogen or lower alkyl of 1-4 carbons;

R² is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted aryl of 6-14 carbons, substituted or unsubstitutedaraliphatic of 7-22 carbons, 2-cyanoethyl or a radical of the formula##STR3## where R and R¹ are as previously defined;

R³ is a direct bond, a substituted or unsubstituted aliphatic diradicalof 1-20 carbons, a substituted or unsubstituted aryl diradical of 6-12carbons, a substituted or unsubstituted alicyclic diradical of 5-12carbons or a substituted or unsubstituted araliphatic diradical of 7-22carbons, where the diradical may contain 1-6 --O--, --S-- or --NH--heteroatoms, with the proviso that multiple heteroatoms must beseparated from each other and the diradical ends by at least one carbonatom;

R² and R³ may be linked together to form a 5-membered lactam ring;

R⁴ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons or substituted orunsubstituted araliphatic of 7-22 carbons;

when n is 1, R⁵ is --N═C(R¹¹)(R¹²), --N(R¹³)(R¹⁴) or --N(R⁶)--Q--R¹⁵,

when n is 2, R⁵ is --N(R⁶)--Q--R¹⁷ --Q--N(R⁶)--;

Q is --C(═O)--, --C(═O)--O--, --C(═O)--N(R⁴)--, --C(═S)--N(R⁴)-- or--S(═O)₂ --, in which R⁴ is as previously defined;

R⁶ and R⁷ are independently hydrogen, substituted or unsubstitutedaliphatic of 1-20 carbons, substituted or unsubstituted alicyclic of5-12 carbons, substituted or unsubstituted aryl of 6-14 carbons orsubstituted or unsubstituted araliphatic of 7-22 carbons;

R⁸ is substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted aryl of 6-14 carbons or substituted or unsubstitutedaraliphatic of 7-22 carbons;

R⁹ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted aryl of 6-14 carbons or substituted or unsubstitutedaraliphatic of 7-22 carbons;

R¹⁰ is hydrogen or aliphatic of 1-4 carbons;

R¹¹ and R¹² are independently hydrogen, substituted or unsubstitutedaliphatic of 1-20 carbons, substituted or unsubstituted alicyclic of5-12 carbons, substituted or unsubstituted aryl of 6-14 carbons,substituted or unsubstituted araliphatic of 7-22 carbons;

R¹¹ and R¹² may be linked together to form a substituted orunsubstituted alicyclic ring of 5-12 carbons or may be linked togetherthrough an --O--, --S-- or --NH-- heteroatom to form a heterocyclic ringof 5-12 atoms wherein the --NH-- may be substituted by lower alkyl of1-4 carbons;

R¹³ is hydrogen, substituted or unsubstitued aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted araliphatic of 7-22 carbons or substituted orunsubstituted aryl of 6-14 carbons, where the R¹³ substituents arechloro, bromo, cyano, hydroxy, epoxy, alkyl of 1-20 carbons, cycloalkylof 5-12 carbons, aryl of 6-14 carbons, aralkyl of 7-22 carbons, alkoxyof 1-20 carbons, cycloalkoxy of 5-12 carbons, aryloxy of 6-14 carbons,aralkoxy of 7-15 carbons, aliphatic acyloxy of 2-20 carbons, alicyclicacyloxy of 6-13 carbons, aryl acyloxy of 7-15 carbons, alkylthio of 1-12carbons, trialkoxysilyl of 3-12 carbons or araliphatic acyloxy of 8-16carbons, wherein any alkyl or cycloalkyl substituent group may containisolated double bonds;

R¹⁴ is substituted or unsubstitued aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted araliphatic of 7-22 carbons or substituted orunsubstituted aryl of 6-14 carbons, where the R¹⁴ substituents arechloro, bromo, cyano, hydroxy, epoxy, alkyl of 1-20 carbons, cycloalkylof 5-12 carbons, aryl of 6-14 carbons, aralkyl of 7-22 carbons, alkoxyof 1-20 carbons, cycloalkoxy of 5-12 carbons, aryloxy of 6-14 carbons,aralkoxy of 7-15 carbons, aliphatic acyloxy of 2-20 carbons, alicyclicacyloxy of 6-13 carbons, aryl acyloxy of 7-15 carbons, alkylthio of 1-12carbons, trialkoxysilyl of 3-12 carbons or araliphatic acyloxy of 8-16carbons, wherein any alkyl or cycloalkyl substituent group may containisolated double bonds;

R¹⁵ is hydrogen, substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted aryl of 6-14 carbons or substituted or unsubstitutedaraliphatic of 7-22 carbons;

When Q is --C(═O)--, R¹⁵ may also be2-(3,5-dialkyl-4-hydroxyphenyl)ethyl of 13-21 carbons,3,5-dialkyl-4-hydroxyphenyl of 11-19 carbons in which the alkyl groupsare branched or unbranched alkyl of 1-8 carbons,4-benzoyl-3-hydroxyphenoxymethyl, 2-alkylthioethyl of 3-20 carbons,alkylthiomethyl of 2-20 carbons, 2-(dialkylaminoalkylthio)ethyl of 5-30carbons or R¹⁶ --NH--C(═O)--R³ --, in which R³ is as previously definedand R¹⁶ is as defined below;

When Q is --C(═O)--O--, R¹⁵ may also be2,2,6,6-tetramethyl-4-piperidinyl, in which the piperidinyl nitrogen isunsubstituted or substituted with methyl, ethyl, allyl, oxyl, hydroxyl,benzyl, benzoyl or acetyl; 2-(3-hydroxy-4-benzoylphenoxy)ethyl;2-acryloyloxyethyl; 2-methacryloyloxyethyl;2-(3-hydroxy-4-benzotriazol-2-ylphenoxy)ethyl;3-(3-benzotriazol-2-yl-4-hydroxyphenyl)propyl, in which thebenzotriazolyl may be substituted in the 5 position with chlorine,methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl and the phenyl groupmay be substituted ortho to the hydroxy group with an alkyl group of11-12 carbons or an aralkyl group of 9-12 carbons;2-(3,5-dialkyl-4-hydroxyphenyl)ethyl of 13-21 carbons,3-(3,5-dialkyl-4-hydroxyphenyl)propyl of 14-22 carbons or2-[3-(3,5-dialkyl-4-hydroxyphenyl)propionyl-oxy]ethyl of 16-24 carbons,in which the alkyl groups are branched or unbranched alkyl groups of 1-8carbons; with the proviso that when Q is --C(═O)--O--, R¹⁵ is nothydrogen;

R¹⁶ is substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted aryl of 6-14 carbons, substituted or unsubstitutedaraliphatic of 7-22 carbons, 3,5-dialkyl-4-hydroxyphenyl of 11-19carbons in which the alkyl groups are independently branched orunbranched alkyl of 1-8 carbons or 2,2,6,6-tetramethyl-4-piperidinyl, inwhich the nitrogen may be substituted with methyl, ethyl, allyl, oxyl,hydroxyl, benzyl, benzoyl or acetyl; and

R¹⁷ is a substituted or unsubstituted aliphatic diradical of 1-20carbons, substituted or unsubstituted aryl diradical of 6-12 carbons,substituted or unsubstituted alicyclic diradical of 5-12 carbons orsubstituted or unsubstituted araliphatic diradical of 7-22 carbons,where the diradicals may contain 1-6 --O--, --S-- or --NH-- heteroatoms,with the proviso that multiple heteroatoms must be separated from eachother and the diradical ends by at least one carbon atom; substituentsfor any of R, R², R³, R⁴, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², R¹⁵, R¹⁶ or R¹⁷ maybe one or more of chloro, bromo, alkyl of 1-8 carbons, alkoxy of 1-8carbons, phenoxy, cyano, hydroxy, epoxy, carboxy, alkoxycarbonyl of 2-6carbons, alkanoyloxy of 1-4 carbons, alkanoyl of 1-4 carbons, acryloyl,acryloyloxy, methacryloyl, methacryloyloxy, hydroxymethyl,2-hydroxyethyl, alkylthio of 1-4 carbons or trialkoxysilyl of 3-12carbons, with the proviso that when Q is --C(═O)--, R¹⁵ may not besubstituted with a carboxy group; and where R is 2-hydroxy substitutedaliphatic or 2-hydroxy substituted alicyclic, R may also be substitutedby aliphatic of 1-20 carbons, alicyclic of 5-12 carbons, aryl of 6-14carbons, araliphatic of 7-22 carbons, alkoxy of 1-20 carbons,cycloalkoxy of 5-12 carbons, aryloxy of 6-14 carbons, aralkoxy of 7-15carbons, aliphatic acyloxy of 2-20 carbons, alicyclic acyloxy of 6-13carbons, aryl acyloxy of 7-15 carbons or araliphatic acyloxy of 8-16carbons, where any alkyl or cycloalkyl substituent group of the2-hydroxy substituted group may contain isolated double bonds.

Preferably, R is hydrogen, substituted or unsubstituted alkyl of 1-10carbons, substituted or unsubstituted alkenyl of 3-8 carbons,substituted or unsubstituted benzyl, 2-cyanoethyl, acetyl, substitutedor unsubstituted benzoyl, 2-hydroxyalkyl of 2-10 carbons,2-hydroxy-3-phenoxypropyl or 2-hydroxy-3-(2-ethylhexoxy)propyl.

More preferably, R is hydrogen, methyl, acetyl or benzoyl.

Preferably, R¹ is hydrogen or methyl and is more preferably hydrogen.

Preferably, R² is hydrogen, alkyl of 1-4 carbons or a2,2,6,6-tetramethyl-4-piperidinyl radical, or may be linked with R³ toform a 5-membered lactam ring.

More preferably, R² is hydrogen.

Preferably, R³ is a direct bond, an alkylene diradical of 1-8 carbons oran o-, m- or p-phenylene diradical, or may be linked with R² to form a5-membered lactam ring.

More preferably, R³ is a direct bond or an alkylene diradical of 1-7carbons.

Preferably, R⁴ is hydrogen.

Preferably, Q is --C(═O)--, --C(═O)--O--, or --C(═O)--N(R⁴)--, and morepreferably, Q is --C(═O)-- or --C(═O)--NH--.

Preferably, R⁶ and R⁷ are independently hydrogen, substituted orunsubstituted aliphatic of 1-8 carbons, substituted or unsubstitutedphenyl or substituted or unsubstituted benzyl.

More preferably, R⁶ is hydrogen, methyl or ethyl and R⁷ is substitutedor unsubstituted aliphatic of 1-8 carbons or substituted orunsubstituted phenyl.

Preferably, R⁸ is substituted or unsubstituted aliphatic of 1-8 carbons,substituted or unsubstituted phenyl or substituted or unsubstitutedbenzyl.

More preferably, R⁸ is substituted or unsubstituted alkyl of 1-4carbons.

Preferably, R⁹ is hydrogen, substituted or unsubstituted aliphatic of1-8 carbons, substituted or unsubstituted phenyl or substituted orunsubstituted benzyl.

Preferably, R¹¹ and R¹² are independently hydrogen, alkyl of 1-8carbons, cycloalkyl of 5-8 carbons, substituted or unsubstituted aryl of6-12 carbons where the substituents are hydroxy or lower alkyl of 1-4carbons, or R¹¹ and R¹² may be linked together to form an alicyclic ringof 5-8 carbons or may be linked together through a nitrogen atom to forma 2,2,6,6-tetramethyl-4-piperidinyl ring.

More preferably, R¹¹ and R¹² are independently lower alkyl of 1-4carbons or may be linked together to form a cyclopentyl, cyclohexyl orcyclooctyl ring or may be linked together through a nitrogen atom toform a 2,2,6,6-tetramethyl-4-piperidinyl ring.

Preferably, R¹³ is hydrogen, alkyl of 1-10 carbons, cycloalkyl of 5-8carbons, aralkyl of 7-9 carbons, phenyl, substituted or unsubstituted2-hydroxyalkyl of 2-12 carbons or substituted or unsubstituted2-hydroxycycloalkyl of 5-8 carbons where the substituents may be alkylof 1-8 carbons, cycloalkyl of 5-8 carbons, aryl of 6-10 carbons, alkoxyof 1-8 carbons, aryloxy of 6-14 carbons, aliphatic acyloxy of 2-8carbons, cycloaliphatic acyloxy of 6-9 carbons, aryl acyloxy of 7-10carbons or araliphatic acyloxy of 8-10 carbons.

More preferably, R¹³ is hydrogen, alkyl of 1-4 carbons, cyclohexyl,benzyl, phenyl, substituted or unsubstituted 2-hydroxyalkyl of 2-10carbons or 2-hydroxycyclohexyl where the substituents may be alkyl of1-8 carbons, phenoxy, acetoxy, acryloyloxy, methacryloyloxy orbenzoyloxy.

Preferably, R¹⁴ is alkyl of 1-10 carbons, cycloalkyl of 5-8 carbons,aralkyl of 7-9 carbons, phenyl, substituted or unsubstituted2-hydroxyalkyl of 2-12 carbons or substituted or unsubstituted2-hydroxycycloalkyl of 5-8 carbons where the substituents may be alkylof 1-8 carbons, cycloalkyl of 5-8 carbons, aryl of 6-10 carbons, alkoxyof 1-8 carbons, aryloxy of 6-14 carbons, aliphatic acyloxy of 2-8carbons, cycloaliphatic acyloxy of 6-9 carbons, aryl acyloxy of 7-10carbons or araliphatic acyloxy of 8-10 carbons.

More preferably, R¹⁴ is alkyl of 1-4 carbons, cyclohexyl, benzyl,phenyl, substituted or unsubstituted 2-hydroxyalkyl of 2-10 carbons or2-hydroxycyclohexyl where the substituents may be alkyl of 1-8 carbons,phenoxy, acetoxy, acryloyloxy, methacryloyloxy or benzoyloxy.

Preferably, R¹⁵ is aliphatic of 1-18 carbons, aryl of 6-12 carbons,aralkyl of 7-18 carbons or cycloalkyl of 6-8 carbons; and when Q is--C(═O)--, R¹⁵ is preferably also 3,5-di-t-alkyl-4-hydroxyphenyl of14-18 carbons, 2-(3,5-di-t-alkyl-4-hydroxyphenyl)ethyl of 16-20 carbons,4-benzoyl-3-hydroxyphenoxymethyl, 2-alkylthioethyl of 8 to 20 carbons orR¹⁶ --NH--C(═O)--R³ --, where R³ is a direct bond or a 1,2-ethylenediradical, R¹⁶ is hydrogen, alkyl of 1-12 carbons, aryl of 6-10 carbons,3,5-di-t-alkyl-4-hydroxyphenyl of 14-18 carbons or2,2,6,6-tetramethyl-4-piperidinyl, in which the piperidinyl nitrogen maybe substituted with methyl or acetyl; and when Q is --C(═O)--O--, R¹⁵ isalso preferably 2,2,6,6-tetramethyl-4-piperidinyl in which thepiperidinyl nitrogen is unsubstituted or substituted with methyl,benzoyl or acetyl;

2-(3-hydroxy-4-benzoylphenoxy)ethyl;

2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl;

3-(3,5-di-t-butyl-4-hydroxyphenyl)propyl;

2-(3-hydroxy-4-benzotriazol-2-ylphenoxy)ethyl;

2-acryloyloxyethyl; and 2-methacryloyloxyethyl.

More preferably, R¹⁵ is methyl, ethyl, propyl, isopropyl, butyl, pentyl,hexyl, heptyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl,octadecyl, phenyl, 2-hydroxyphenyl, dimethyl-m-isopropenylbenzyl; andwhen Q is --C(═O)--, R¹⁵ is also more preferably3,5-di-t-butyl-4-hydroxyphenyl, 2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl,4-benzoyl-3-hydroxyphenoxymethyl, undecyl, heptadecyl or R¹⁶--NH--C(═O)--R³, where R³ is a direct bond and R¹⁶ is3,5-di-t-butyl-4-hydroxyphenyl or 2,2,6,6-tetramethyl-4-piperidinyl; andwhen Q is --C(═O)--O--, R¹⁵ is also more preferably allyl, methallyl,2,2,6,6-tetramethyl-4-piperidinyl, 1,2,2,6,6-pentamethyl-4-piperidinyl,or 2-(3-hydroxy-4-benzoylphenoxy)ethyl.

Preferably, R¹⁷ is an aliphatic diradical of 2-12 carbons, acycloalkylene diradical of 5-12 carbons, an alicyclic diradical of 7-12carbons, an aryl diradical of 6-12 carbons or an aralkylene diradical of7-12 carbons.

More preferably, R¹⁷ is an alkylene diradical of 2-10 carbons or an o-,m-, or p-phenylene diradical which may be substituted with a methylgroup, cycloalkylene of 9-10 carbons or aralkylene of 8-12 carbons.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The novel derivatives of N-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acidhydrazides of the present invention contain both a hindered amine lightstabilizing group and an amic acid hydrazide derivative. The amic acidhydrazide derivative enhances the photooxidative stabilizing propertiesof the hindered amine groups and imparts thermooxidative stabilizing andmetal complexing properties to the compounds. By careful selection ofthe derivative, the compatibility of the novel compounds with varioushost resins to be stabilized can be increased. The novel compounds ofthe present invention have low volatility and are not readily lost frompolymeric systems via volatilization, exudation, migration orextraction.

GENERIC GROUP EXAMPLES

The present invention comprises a compound which is a N-HALS-substitutedamic acid hydrazide derivative of structural Formula I set forth in theabove Summary of the Invention. The Summary also sets forth preferredand more preferred embodiments of the various constituent groups of thecompound. Specific, non-limiting examples of particular constituentgroups are as follows:

As a substituted or unsubstituted aliphatic of 1-20 carbons R, R², R⁴,R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ may be, for example,methyl, ethyl, n-propyl, isopropyl, allyl, hexyl, heptyl, octyl, nonyl,decyl, propargyl, octadecyl, dodecyl, isododecyl, tetradecyl,2-methallyl, 2-hexenyl, 10-undecenyl, 2-dodecenyl, n-butyl,2-hydroxyethyl, 2-butenyl, 2-hydroxypropyl, cyanomethyl,2,3-epoxypropyl, dimethylaminoethyl, 2-hydroxy-3-phenoxypropyl,2-hydroxy-3-(2-ethylhexoxy)propyl or 2-hydroxyoctyl.

As a substituted or unsubstituted alicyclic of 5-12 carbons, R, R², R⁴,R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ may be, for example,cyclohexyl, trimethylcyclohexyl, cyclooctyl, cyclododecyl,4-t-butylcyclohexyl, 3-cyclohexenyl, cyclododecyl, 4-octylcyclohexyl or2-methyl-4-octylcyclohexyl.

As substituted or unsubstituted aryl of 6-14 carbons, R², R⁶, R⁷, R⁸,R⁹, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ may be for example phenyl tolyl,4-chlorophenyl, isopropylphenyl, anisyl, 3,5-di-t-butyl-4-hydroxyphenyl,naphthyl, 3-methyl-5-t-butyl-4-hydroxyphenyl, 3,4,5-trimethoxyphenyl or4-dimethylaminophenyl.

As a substituted or unsubstituted araliphatic group of 7-22 carbons, R,R², R⁴, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ may be, forexample, benzyl, 3-methylbenzyl, 4-t-butylbenzyl, cinnamyl,3,5-di-t-butyl-4-hydroxybenzyl, 2-phenylethyl, cumyl, trimethylbenzyl,4-octyloxybenzyl, naphthylmethyl or (4-dodecylphenyl)methyl.

As a substituted or unsubstituted aliphatic acyl of 2-20 carbons,substituted or unsubstituted alicyclic acyl of 7-16 carbons, substitutedor unsubstituted aryl acyl of 7-11 carbons or substituted orunsubstituted araliphatic acyl of 7-22 carbons, R may be, for example,formyl, acetyl, chloroacetyl, acryloyl, methacryloyl, propionyl,butyryl, 2-methylpropionyl, caproyl, capryloyl, lauroyl, crotonoyl,stearoyl, cyclohexylcarbonyl, 4-t-butylcyclohexylcarbonyl,3-cyclohexeny-1-carbonyl, cyclododecylcarbonyl,4-octylcyclohexylcarbonyl, 2-ethoxy-2-oxoacetyl, 2-methoxy-2-oxoacetyl,2-methyl-4-octylcyclohexylcarbonyl, benzoyl, toluoyl, 4-chlorobenzoyl,isopropylbenzoyl, anisoyl, 3,5-di-t-butyl-4-hydroxybenzoyl, naphthoyl,3-methyl-5-t-butyl-4-hydroxybenzoyl, 3,4,5-trimethoxybenzoyl,4-dimethylaminobenzoyl, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl,cinnamoyl or dihydrocinnamoyl. R is preferably alkanoyl of 2-5 carbons,cyclohexylcarbonyl, benzoyl or phenacyl.

As --C(═O)--N(R⁶)(R⁷), R may be, for example, N-methylcarbamoyl,N-(n-butyl)carbamoyl, N-dodecylcarbamoyl, N,N-dimethylcarbamoyl,N,N-diethylcarbamoyl, N,N-di(n-hexyl)carbamoyl, piperidin-1-ylcarbonyl,2,2,6,6-tetramethyl-4-piperidinylcarbonyl, piperazine-1-carbonyl,4-methylpiperazine-1-carbonyl, morpholin-1-carbonyl,2-(dibutylamino)-2-oxoacetyl, 2-(phenylamino)-2-oxoacetyl,N-phenylcarbamoyl, N-(4-butylphenyl)carbamoyl,N-(alphanaphthyl)carbamoyl, N-phenyl-N-hexylcarbamoyl,N-(trimethylphenyl)-N-amylcarbamoyl, N,N-diphenylcarbamoyl,N,N-di(4-methylphenyl)carbamoyl orN-(4-benzylaminophenyl)-N-phenylcarbamoyl.

As --(C(═O))_(a) --O--R⁸, R may be, for example, methoxycarbonyl,2-ethoxy-2-oxoacetyl, 2-methoxy-2-oxoacetyl,2-cyclohexyloxy-2-oxoacetyl, ethoxycarbonyl, phenoxycarbonyl,(2-methylphenoxy)carbonyl, allyloxycarbonyl, cyclododecyloxycarbonyl,2-ethylhexoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl or(4-octyloxyphenyl)carbonyl.

As --(CH₂)_(a) --C(═O)--O--R⁹, R may be, for example,ethoxycarbonylmethyl, methoxycarbonylmethyl, methoxycarbonylethyl,butoxycarbonylmethyl, (benzyloxy)carbonylmethyl or(benzyloxy)carbonylethyl.

As --(CH₂ --CH(R¹)--O)_(b) --R¹⁰, R is, for example,nonylphenoxypoly(ethoxy)ethyl, butoxypoly(propoxy)ethyl,hydroxypoly(ethoxy)ethyl or 2-[hydroxypoly(propoxy)]-2-methylethyl.

As a lower alkyl group of 1-4 carbons, R¹ may be, for example, methyl,ethyl, propyl, isopropyl, n-butyl, sec-butyl or t-butyl.

As an aliphatic group of 1-4 carbons, R¹⁰ may be, for example, methyl,ethyl, propyl, isopropyl, allyl, n-butyl, sec-butyl or isobutyl.

As a substituted or unsubstituted aliphatic diradical of 1-20 carbons, asubstituted or unsubstituted aryl diradical of 6-12 carbons, asubstituted or unsubstituted alicyclic diradical of 5-12 carbons or asubstituted or unsubstituted araliphatic diradical of 7-22 carbonsoptionally containing 1-6 --O--, --S-- or --NH-- heteroatoms, R³ and R¹⁷may be, for example, methylene, ethane-1,2-diyl, ethene-1,2-diyl,propane-1,3-diyl, propene-1,2-diyl, 2-thiopropene-1,3-diyl,2-oxapropane-1,3-diyl, hexane-1,3-diyl, 2-azapropane-1,3-diyl,2-methyl-2-azapropane-2,3-diyl, cyclohexane-1,2-diyl, 1,2-phenylene,1,3-phenylene, 1,4-phenylene, hexane-1,6-diyl, octane-1,8-diyl,decane-1,10-diyl, dodecane-1,12-diyl, 3-hexen-1,6-diyl,4-methyl-l,2-phenylene, 4-chloro-1,2-phenylene,4-methylcyclohexane-1,2-diyl, cyclohexane-1,2-diyl,4-methyl-4-cyclohexane-1,2-diyl, toluene-alpha,2-diyl,toluene-alpha,4-diyl or toluene-alpha,3-diyl.

As a substituted or unsubstituted 2-hydroxyalkyl of 2-20 carbons orsubstituted or unsubstituted 2-hydroxycycloalkyl of 5-12 carbons, R¹³and R¹⁴ may be, for example, 2-hydroxyethyl, 2-hydroxypropyl,2-hydroxybutyl, 1-methyl-2-hydroxypropyl, 2-hydroxycyclododecyl,2-hydroxydecyl, 2-hydroxycyclohexyl, 2-hydroxycyclopentyl,2-hydroxydodecyl, 2-hydroxy-2-phenylethyl, 2-hydroxyhexadecyl,2-hydroxyhexyl, 2-hydroxy-5-hexenyl, 2-hydroxyoctadecyl,2-hydroxy-3-methacryloyloxypropyl, 2-hydroxy-3-acryloyloxypropyl,2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-(4-methoxyphenoxy)propyl,2-hydroxy-3-isopropoxypropyl, 2-hydroxy-3-methoxypropyl,2-hydroxy-3-(2-ethylhexoxy)propyl, 2-hydroxy-3-benzyloxypropyl or2-hydroxy-3-benzoyloxypropyl.

When R¹¹ and R¹² are linked together to form a substituted orunsubstituted alicyclic ring of 5-12 carbon atoms or are linked togetherthrough a heteroatom to form a heterocyclic ring of 5-12 atoms, wherethe heteroatom is --O--, --S-- or --NH--, the --NH-- being optionallysubstituted by lower alkyl of 1-4 carbons, R¹¹ and R¹² together with thecarbon to which they are attached may form, for example, cyclopentyl,cyclohexyl, cyclohexenyl, cycloheptyl, 4-t-butylcyclohexyl,2-methylcyclohexyl, cyclooctyl, cyclododecyl,2,2,6,6-tetramethyl-4-piperidinyl,2,6-diethyl-2,3,6-trimethyl-4-piperidinyl,1,2,2,6,6-pentamethyl-4-piperidinyl,1-ethyl-2,2,6,6-tetramethyl-4-piperidinyl, 4-oxacyclohexyl or4-thiocyclohexyl rings.

When R² and R³ are linked together to form a 5-membered lactam ring, R²and R³ together with the nitrogen atom to which they are attached mayform, for example, a 1-aza-2-oxocyclopentane-1,4-diyl diradical.

As a 2-(3,5-dialkyl-4-hydroxyphenyl)ethyl group of 13-21 carbons, R¹⁵may be, for example, 2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl,2-(3,5-di-t-amyl-4-hydroxyphenyl)ethyl or2-(3-t-butyl-5-methyl-4-hydroxyphenyl)ethyl.

As a 3,5-dialkyl-4-hydroxyphenyl group of 11-19 carbons, R¹⁵ and R¹⁶ maybe, for example, 3,5-di-t-butyl-4-hydroxyphenyl,3,5-di-t-amyl-4-hydroxyphenyl or 3-t-butyl-5-methyl-4-hydroxyphenyl.

As a 2-alkylthioethyl group of 3-20 carbons, R¹⁵ may be, for example,2-methylthioethyl, 2-hexylthioethyl, 2-octylthioethyl,2-dodecylthioethyl or 2-octadecylthioethyl.

As a 2-alkylthiomethyl group of 2-20 carbons, R¹⁵ may be, for example,methylthiomethyl, ethylthiomethyl, propylthiomethyl, hexylthiomethyl,dodecylthiomethyl or octadecylthiomethyl.

As a 2-(dialkylaminoalkylthio)ethyl group of 5-30 carbons, R¹⁵ may be,for example, 2-(dimethylaminomethylthio)ethyl,2-[2-(dimethylamino)ethylthio]ethyl,2-[3-(dimethylamino)propylthio]ethyl, 2-[2-(diethylamino)ethylthio]ethylor 2-[3-(diethylaminopropylthio)ethyl].

When R¹³, R¹⁴ and R are substituted 2-hydroxyaliphatic or2-hydroxyalicyclic, optional substituents are, for example, methyl,ethyl, propyl, n-butyl, sec-butyl, t-butyl, hexyl, octyl, decyl,dodecyl, octadecyl, allyl, methallyl, cyclopentyl, cyclohexyl,cyclooctyl, cyclododecyl, 4-methylcyclohexyl, phenyl, 4-methoxyphenyl,benzyl, cumyl, phenethyl, 3,5-di-t-butyl-4-hydroxyphenyl,(3,5-di-t-butyl-4-hydroxyphenyl)ethyl, methoxy, ethoxy, propoxy, butoxy,isopropoxy, t-butoxy, hexoxy, 2-ethylhexoxy, dodecyloxy, octadecyloxy,cyclopentoxy, cyclohexoxy, 4-t-butylcyclohexoxy, phenoxy,2,5-di-t-butyl-4-hydroxyphenoxy, benzyloxy,3,5-di-t-butyl-4-hydroxyphenoxy, 3,5-di-t-butyl-4-hydroxybenzyloxy,acetoxy, propionoxy, butyryloxy, lauroyloxy, stearoyloxy,cyclohexanecarbonyloxy, cyclopentanecarbonyloxy, benzoyloxy,3,5-di-t-butyl-4-hydroxybenzoyloxy, 3-phenylpropionoxy, phenylacetyloxy,3-(3,5-di-t-butyl-4-hydroxyphenyl)propionoxy or3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionoxy.

LIST OF ILLUSTRATIVE COMPOUNDS

Non-limiting examples of suitable derivatives of N-HALS-substituted amicacid hydrazides of Formula I include:

(1) 2,2'-[N-(2,2,6,6-tetramethyl-4 piperidinyl)oxamoyl]terephthalic aciddihydrazide

(2)2,2'-[N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]dodecanoicacid dihydrazide

(3)2,2'-[N-(1-methyl-2,2,6,6-tetramethyl-4-piperidinyl)succinamoyl]-1,4-cyclohexylenedicarboxylic acid dihydrazide

(4) 1,4-phenylenebis[2-(N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl)isophthalamoyl)carbazate]

(5) 1,12-dodecamethylenebis[2-(N-methyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)-oxamoyl)carbazate]

(6) 2,2'-[N-(2,2,6,6-tetramethyl-4-piperidinyl)succinamoyl]isophthalicacid dihydrazide

(7)1-[N-n-butyl-N-(1-allyloxycarbonyl-2,2,6,6-tetramethyl-4piperidinyl)succinamoyl]-2-(3,5-di-t-amyl-4-hydroxybenzoyl)hydrazine

(8)N-[1-butoxypoly(propoxy)ethyl-2,2,6,6-tetramethyl-4-piperidinyl)-N'-(t-butylamino)oxamide

(9)N-(1-phenylcarbamoyl-2,2,6,6-tetramethyl-4-piperidinyl)-N'-(cyclohexylamino)isophthalamide

(10)1-(N-[1-(2-ethoxy-2-oxoacetyl)-2,2,6,6-tetramethyl-4-piperidinyl]oxamoyl)-2-(n-butylcarbamoyl)hydrazine

(11)1-(N-[1-(2-methoxy-2-oxoacetyl)-2,2,6,6-tetramethyl-4-piperidinyl]azelamoyl)-2-(cyclohexylcarbamoyl)hydrazine

(12)1-(N-[1-(methoxycarbonylmethyl)-2,2,6,6-tetramethyl-4-piperidinyl]oxamoyl)-1-methyl-2-(benzylcarbamoyl)hydrazine

(13)1-(N-[1-(3,5-di-t-butyl-4-hydroxybenzyl)-2,2,6,6-tetramethyl-4-piperidinyl]oxamoyl)-2-[3-(hexylthio)propionyl]hydrazine

(14)1-[N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-acetylhydrazine

(15)1-[N-(1-benzoyl-2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2benzoylhydrazine

(16)1-[N-(2-cyanoethyl)-N-(1-(2-cyanoethyl)-2,2,6,6-tetramethyl-4-piperidinyl)succinamoyl]-2-(cyclohexoxycarbonyl)hydrazine

(17)1-[N-(1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinyl)adipamoyl]-2-(phenoxycarbonyl)hydrazine

(18)1-[N-phenyl-N-(1-dimethylcarbamoyl-2,2,6,6-tetramethyl-4-piperidinyl)terephthalamoyl]-2-dodecanoylhydrazine

(19)1-benzyl-1-[N-benzyl-N-(1-n-butylcarbamoyl-2,2,6,6-tetramethyl-4-piperidinyl)-oxamoyl]-2-benzylhydrazine

(20)1-cyclohexyl-1-[N-(1-ethoxycarbonyl-2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[3-(dodecylthio)propionyl]hydrazine

(21)1-[N-(1-oxyl-2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-(methylcarbamoyl)hydrazine

(22)1-[N-(1-hydroxyl-2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-octanoylhydrazine

(23)1-[N-(2,6-diethyl-1,2,3,6-tetramethyl-4-piperidinyl)oxamoyl]-2-(dimethylcarbamoyl)hydrazine

(24)1-[N-ethyl-N-(1-ethyl-2,2,6,6-tetramethyl-4-piperidinyl)succinamoyl]-2-decanoylhydrazine

(25)N-n-butyl-N-(1-allyl-2,2,6,6-tetramethyl-4-piperidinyl)-N'-(phenylamino)oxamide

(26)N-methyl-N-(1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl)-N'-(diethylamino)oxamide

(27)1-[N-cyclohexyl-N-(1-cyclohexyl-2,2,6,6-tetramethyl-4-piperidinyl)adipamoyl]-2-methyl-2-(n-propylcarbamoyl)hydrazine

(28)1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)-3,3'-thiodipropionamoyl]-2-(benzyloxycarbonyl)hydrazine

(29)1-n-Butyl-1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)-3-oxapimelamoyl]-2-formylhydrazine

(30)1-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-1-[N,N-bis(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-3-azapimelamoyl]-2-propionylhydrazine

(31)1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)succinamoyl]-2-methyl-2-(p-methylphenylcarbamoyl)hydrazine

(32)1-methyl-1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-ethyl-2-(octadecylcarbamoyl)hydrazine

(33)1-(N-[1-(3,5-di-t-butyl-4-hydroxybenzoyl)-2,2,6,6-tetramethyl-4-piperidinyl]oxamoyl)-2-(3,5-di-t-butyl-4-hydroxybenzoyl)hydrazine

(34)1-(N-[1-(3-[3,5-di-t-butyl-4-hydroxyphenyl]propionyl)-2,2,6,6-tetramethyl-4-piperidinyl]succinamoyl)-2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine

(35)1-[N-cyclohexyl-N-(1-cyclohexylcarbonyl-2,2,6,6-tetramethyl-4-piperidinyl)malonamoyl]-2-(cyclohexylcarbonyl)hydrazine

(36)1-[N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-dodecanoylhydrazine

(37)1-[N,N-bis(1-methyl-2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-(n-butylcarbamoyl)hydrazine

(38) N-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-(dimethylamino)oxamide

(39)N-[1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinyl]-N'-[di-(2-hydroxyethyl)amino]oxamide

(40)1-[N-ethyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)azelamoyl]-2-(dimethylthiocarbamoyl)hydrazine

(41)1-methyl-1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-propionylhydrazine

(42)1-[N-(1,2,2,6,6-pentamethyl-4-piperidinyl)oxamoyl]-2-[3-(3,5-di-t-amyl-4-hydroxyphenyl)propionyl]hydrazine

(43) 1-(N-[1-(3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionyl)-2,2,6,6-tetramethyl-4-piperidinyl]oxamoyl]-2-[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionyl]hydrazine

(44)1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[3-(2-dimethylaminoethylthio)propionyl]hydrazine

(45)1,2-bis[N-(1-methyl-2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]hydrazine

(46)1,2-bis[N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)succinamoyl]hydrazine

(47)1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[N-(octadecyl)oxamoyl]hydrazine

(48)1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)succinamoyl]-2-[N-(dodecyl)oxamoyl]hydrazine

(49)1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[N-(3,5-di-t-butyl-4-hydroxyphenyl)succinamoyl]hydrazine

(50)1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[2-(3-hydroxy-4-benzotriazol-2-ylphenoxy)ethoxycarbonyl]hydrazine

(51)1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[3-(3-benzotriazol-2-yl-4-hydroxy-5-t-butylphenyl)propoxycarbonyl]hydrazine

(52)1-[N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2(allyloxycarbonyl)hydrazine

(53)1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)succinamoyl]-2-[2-(acryloyloxy)ethoxycarbonyl]hydrazine

(54)1-[N-(1,2,2,6,6-pentamethyl-4-piperidinyl)oxamoyl]-2-[2-(methacryloyloxy)ethoxycarbonyl]hydrazine

(55)1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethoxycarbonyl]hydrazine

(56)1-[N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)adipamoyl]-2-(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl]hydrazine

(57)1-[N-(1,2,2,6,6-pentamethyl-4-piperidinyl)oxamoyl]-2-(2,2,6,6-tetramethyl-4-piperidinyloxycarbonyl]hydrazine

In addition to the examples of derivatives of N-HALS-substituted amicacid hydrazides set forth above, the hydrazone derivatives resultingfrom the reaction ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminooxamide orN-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminosuccinamide with2-decanone, cyclododecanone, cyclopentanone, 1,3-diphenylacetone,dihydroisophorone, acetophenone, 4-piperidone, formaldehyde,acetaldehyde, salicylaldehyde or methyl cyclohexyl ketone are furthernon-limiting examples of illustrative compounds of the presentinvention.

PREPARATIVE METHODS

The compounds of the present invention, designated generally by FormulaI, may be prepared by various methods, including one or more of themethods as follows. As indicated by variations within the formulas andmethods, different methods may be preferred for use with differentvariations of Formula I.

Preparation of Starting Materials

The preparation of the N-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acidhydrazide starting materials of Formula II (where R² and R³ are notlinked together) are disclosed in copending U.S. Pat. No. 4,983,738, thedisclosure of which is incorporated herein by reference. ##STR4##

The cyclic lactams (i.e., the compounds of Formula II where R² and R³are linked together to form a 5-membered cyclic lactam) may be preparedby reacting 4-amino-2,2,6,6-tetraalkylpiperidines with dialkylitaconates to form an intermediate4-(alkoxycarbonyl)-1-(2,2,6,6-tetraalkyl-4-piperidinyl)-2-pyrrolidoneaccording to the procedure described in U.S. Pat. No. 4,309,546, thedisclosure of which is hereby incorporated herein by reference. The4-alkoxycarbonyl group can then be converted to a hydrazide group byhydrazinoloysis with excess hydrazine hydrate in methanol, usingstandard reaction conditions.

I. Preparation of Hydrazones

The N-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acid hydrazones of FormulaI where n is 1 and R⁵ is --N═C(R¹¹)(R¹²), designated as Formula III, areprepared by one or more of Methods A, B and C as follows.

Preparation Method A

The novel hydrazone derivatives of this invention may be prepared byreacting a hydrazide of Formula II with ketones, aldehydes orformaldehyde in inert solvents, preferably in hydrocarbon solvents underazeotropic conditions.

The reaction sequence of Method A is illustrated by the followingequation: ##STR5##

In the equation for Method A, R, R¹, R², R³, R⁴, R¹¹ and R¹² are aspreviously broadly defined.

Preparation Method B

The novel hydrazone derivatives of the present invention may also beprepared by reacting hydrazones of ketones or aldehydes with esters ofN-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acids of Formula IV, where R¹⁸is lower alkyl of 1 to 4 carbons or phenyl.

The reaction sequence of Method B is illustrated by the followingequation: ##STR6##

R, R¹, R², R³, R¹¹, R¹² and R¹⁸ are as previously broadly defined.

Preparation Method C

The hydrazone derivatives where R³ is a direct bond may also be preparedby reacting hydrazones of ketones or aldehydes with oxalate diesters toform the intermediate of Formula V, which is then reacted with4-amino-2,2,6,6-tetraalkylpiperidines.

The reaction sequence of Method C is illustrated by the followingequations: ##STR7##

In the equation for Method C, R, R¹, R², R¹¹, R¹² and R¹⁸ are aspreviously defined and R³ is a direct bond.

II. Preparation of Carbamoyl and Thiocarbamoyl Derivatives

The novel carbamoyl and thiocarbamoyl derivatives ofN-(2,2,6,6-tetraalkyl-4-piperidinyl) amic acids of Formula I, designatedas Formulas VI and VII, respectively, may be prepared by one or more ofMethods D, E or F, as follows.

Preparation Method D

The novel carbamoyl and thiocarbamoyl derivatives, designated asFormulas VI and VII, where n is 1 and 2, respectively, and R⁵ is--N(R⁶)--Q--R¹⁵ or --N(R⁶)--Q--R¹⁷ --Q--N(R⁶)-- and Q is --C(═O)NH-- or--C(═S)NH--, may be prepared by reacting a hydrazide of Formula II withisocyanates, isothiocyanates, diisocyanates or diisothiocyanates inaprotic polar solvents, such as tetrahydrofuran (THF) ordimethylformamide (DMF).

The reaction sequences of Method D are illustrated by the followingequations: ##STR8##

X is O or S and R, R¹, R², R³, R⁴, R¹⁵ and R¹⁷ are as previously broadlydefined.

Preparation Method E

The novel carbamoyl and thiocarbamoyl derivatives of Formula VI, whereR⁵ is --N(R⁶)--Q--R¹⁵ and Q is --C(═O)--NH-- or --C(═S)--NH--, may alsobe prepared by reacting semicarbazides or thiosemicarbazides with estersof Formula IV of N-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acids.

The reaction sequence of Method E is illustrated by the followingequation: ##STR9##

X is O or S, and R, R¹, R², R³, R⁴, R¹⁵ and R¹⁸ are as previouslybroadly defined.

Preparation Method F

Carbamoyl or thiocarbamoyl derivatives of Formula VIA, where R³ is adirect bond, R⁵ is --N(R⁶)--Q--R¹⁵ and Q is --C(═O)--NH-- or--C(═S)--NH--, may also be prepared by reacting semicarbazides orthiosemicarbazides with oxalate diesters to form the intermediate ofFormula VIII which is then reacted with4-amino-2,2,6,6-tetraalkylpiperidines.

The reaction sequence of Method F is illustrated by the followingequations: ##STR10##

X is O or S and R, R¹, R², R⁴, R¹⁵ and R¹⁸ are as previously defined andR³ is a direct bond.

The reactions of hydrazides with ketones, aldehydes, isocyanates,diisocyanates, isothiocyanates and diisothiocyanates are well known inthe art and can occur under a wide range of conditions, includingvarying temperatures, times, solvents and concentrations. Generally, amole ratio of about 0.9 to about 1.0 to about 1.1 to about 1.0 of thehydrazide to the monofunctional co-reactant is employed. If theco-reactant is difunctional, then a mole ratio of about 1.8 to about 2.0to about 1.1 to about 1.0 of the hydrazide to the difunctionalco-reactant is employed. If the co-reactant is a compound that caneasily be removed from the product by volatalization, for example,acetone or methyl ethyl ketone, lower mole ratios may be desirable. Infact, it may be desirable to use the co-reactant as the solvent.

III. Miscellaneous Reactions

The starting hydrazides of Formula II also react with unsubstituted orN-substituted amic acid esters in lower alcohol solutions to form1,2-amoyl hydrazines, Formula IX, as indicated by the following reactionequation: ##STR11##

The reactions are normally carried out in refluxing methanol but may becarried out in higher boiling aprotic solvents or without a solvent byheating a mixture of the two components above their melting points. Themethyl and ethyl esters of N-substituted oxamates and succinamates arethe preferred co-reactants and R, R¹, R², R³, R⁴, R¹⁵ and R¹⁸ are aspreviously broadly defined.

The novel acyl derivatives of Formula II, designated as Formula X, maybe prepared by reacting the esters of Formula IV with acid hydrazidesneat or in refluxing alcohols, such as methanol, ethanol or isopropanol,as indicated in the following reaction equation: ##STR12##

R, R¹, R², R³, R⁴, R¹⁵ and R¹⁸ are as previously broadly defined.

The novel acyl derivatives of Formula X may also be prepared by reactingthe hydrazides of Formula II with non-cyclic carboxylic acid anhydrides,as indicated per the following equation: ##STR13##

The reactions are typically conducted in aprotic solvents, such as THF,diethyl ether or t-butyl methyl ether. However, the reaction may also becarried out by adding the anhydride to a methanolic solution of thehydrazide. R, R¹, R², R³, R⁴, R¹⁵ and R¹⁸ are as previously broadlydefined. Preferably, R¹⁵ is alkyl of 1-10 carbons or phenyl. Inaddition, when R is hydrogen, alkyl, cycloalkyl, aralkyl or aryl, thecarboxylic acid generated in the reaction may form a salt, designated asFormula XA, with the hindered amine of Formula X, as per the followingequation: ##STR14##

The free base acyl derivatives of Formula X may be regenerated from thecarboxylic acid salt of Formula XA by neutralizing the salt with astronger base than the hindered amine, for example, dilute sodiumhydroxide, dilute potassium hydroxide, hydrazine or more basic amines,such as diethylamine and triethylamine. This neutralization procedure isillustrated by the following equation: ##STR15##

Acyl derivatives, designated as Formula XB where R³ is a direct bond mayalso be prepared by reacting acid hydrazides with oxalate diesters toform the intermediate of Formula XI which is then reacted with4-amino-2,2,6,6-tetraalkylpiperidines, as indicated in the followingreaction equations: ##STR16##

R, R¹, R², R⁴, R¹⁵ and R¹⁸ are as previously defined and R³ is a directbond.

The corresponding diacyl derivatives of starting Formula II, designatedas Formula XII, can be prepared by reacting the amic acid esters ofFormula IV with diacid dihydrazides in a 2:1 mole ratio neat or inrefluxing alcohols, such as methanol, ethanol or isopropanol, asindicated in the following reaction equation: ##STR17##

For the preparation of the novel diacyl derivatives of Formula XII, R,R¹, R², R³, R⁴, R¹⁵, R¹⁷ and R¹⁸ are as previously defined.

The novel alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl andaralkoxycarbonyl derivatives of starting materials of Formula II,designated as Formula XIII, may be prepared by reacting theN-(2,2,6,6-tetraalkyl-4-piperidinyl)amic acid esters of Formula IV withthe corresponding alkyl, cycloalkyl, aryl or aralkyl carbazates inrefluxing methanol, per the following equation: ##STR18##

R, R¹, R², R³, R⁴ and R¹⁵ are as previously broadly defined.

Alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl andaralkoxycarbonyl derivatives of Formula XIIIA where R³ is a direct bondmay also be prepared by reacting alkyl, cycloalkyl, aryl or aralkylcarbazates with oxalate diesters to form the intermediate of Formula XIVwhich is then reacted with 4-amino-2,2,6,6-tetraalkylpiperidines, perthe following equations: ##STR19##

For the preparation of Formula XIIIA, R, R¹, R², R⁴, R¹⁵ and R¹⁸ are aspreviously defined and R³ is a direct bond.

The novel aryloxycarbonyl derivatives of II, designated as Formula XV,may also be prepared by reacting the hydrazides II with diarylcarbonates, per the following equation: ##STR20##

R, R¹, R², R³ and R⁴ are as previously broadly defined and R¹⁹ issubstituted or unsubstituted aryl of 6-12 carbons.

The novel dialkoxycarbonyl, dicycloalkoxycarbonyl, diaryloxycarbonyl anddiaralkoxycarbonyl derivatives of Formula II, designated as Formula XVI,may be prepared by reacting the amic acid esters of Formula IV with thecorresponding bis-carbazates, per the following equation: ##STR21##

R, R¹, R², R³, R⁴, R¹⁵, R¹⁷ and R¹⁸ are as previously defined, unlessotherwise specified.

Sulfonyl derivatives of II, designated as Formulas XVII and XVIII, maybe prepared by reacting the amic acid esters of Formula IV with thecorresponding sulfonyl hydrazides or bis sulfonyl dihydrazides,respectively, per the following equations: ##STR22##

For the preparation of the novel sulfonyl derivatives of Formulas XVIIand XVIII, R, R¹, R², R³, R⁴, R¹⁵, R¹⁷ and R¹⁸ are as previously broadlydefined, unless otherwise specified.

The novel sulfonyl derivatives of Formula XVIIA where R³ is a directbond also may be prepared by reacting sulfonyl hydrazides with oxalatediesters to form the intermediate of Formula XIX which is then reactedwith 4-amino-2,2,6,6-tetralkylpiperidines, per the following equations:##STR23##

R, R¹, R², R⁴, R¹⁵ and R¹⁸ are as previously defined and R³ is a directbond.

The novel 2-hydroxyalkyl derivatives of Formula II, designated asFormulas XX and XXI, may be prepared by reacting the hydrazides ofFormula II with epoxides. The reactions are generally carried out neator in a minimum amount of a high boiling solvent, such asdimethylformamide (DMF), dimethylacetamide (DMAC), xylene or mesitylene,for example. Reaction generally occurs quite readily at 140°-150° C.Illustrative reaction equations are as follows: ##STR24##

R, R¹, R², R³ and R⁴ are as previously broadly defined and R²⁰ and R²¹are independently hydrogen, alkyl of 1-20 carbons, cycloalkyl of 5-12carbons, aryl of 6-12 carbons, aralkyl of 7-20 carbons, alkoxy of 1-20carbons, cycloalkoxy of 5-12 carbons, aryloxy of 6-14 carbons, aralkoxyof 7-15 carbons, aliphatic acyloxy of 2-20 carbons, cycloaliphaticacyloxy of 6-13 carbons, aryl acyloxy of 7-15 carbons, araliphaticacyloxy of 8-16 carbons and in addition, R²⁰ and R²¹ may be linkedtogether to form an alicyclic ring of 5-12 carbons and any alkyl orcycloalkyl group may contain isolated double bonds.

If R is H, a third reaction product, XXII, is obtained: ##STR25##

R is H and R¹, R², R³, R⁴, R²⁰ and R²¹ are as previously broadlydefined.

As indicated, the hydrazide group reacts with two equivalents of epoxideand if the piperidinyl amino group is not substituted, the hinderedamino group will also react with the epoxide to give a trialkylatedproduct. The ratio of the unsubstituted hydrazide of Formula II to themono-, di- and trialkylated products is dependent upon the mole ratio ofepoxide to hydrazide of Formula II, the temperature and theconcentration if the reaction is run in a solvent.

The novel aliphatic, alicyclic, araliphatic and aryl derivatives ofFormula II, designated as Formula XXIII, may be prepared by reactingesters of N-(2,2,6,6-tetraalkyl-4-piperdinyl)amic acids of Formula IVwith monosubstituted hydrazines (R¹³ NHNH₂), 1,1-disubstitutedhydrazines (R¹³ R¹⁴ NNH₂), 1,1,2-trisubstituted hydrazines (R¹³ R¹⁴ NNR⁴H) and 1,2-disubstituted hydrazines (R⁴ NHNHR¹⁴) per the followingequation: ##STR26##

R, R¹, R², R³, R⁴, R¹³, R¹⁴ and R¹⁸ are as previously broadly defined.

The novel aliphatic, alicyclic, araliphatic and aryl derivatives XXIIIAwhere R³ is a direct bond may be prepared by reacting oxalate diesterswith the above-indicated hydrazines to form the intermediate XXIV whichis then reacted with 4-amino-2,2,6,6-tetraalkylpiperidines, per thefollowing equations: ##STR27##

R, R¹, R², R⁴, R¹³, R¹⁴ and R¹⁸ are as previously defined and R³ is adirect bond.

The reactions to prepare the novel aliphatic, alicyclic, araliphatic andaryl derivatives, Formulas XXIII and XXIIIA, are run in polar solventsusing equivalent amounts or a slight excess of the desired hydrazine.Depending upon R³, the reaction may proceed at room temperature or mayrequire refluxing. Preferably, the hydrazinolysis reaction is carriedout in methanol or ethanol at about 10° C. to about 30° C. if R³ is adirect bond and at reflux if R³ is not a direct bond.

The following lists of compounds are to provide specific, butnon-limiting, examples of the various types of starting or intermediatecompounds which can be used in the foregoing illustrative preparativemethods.

Non-limiting examples of suitable ketones include acetone, methyl ethylketone, 2-pentanone, 2-hexanone, 3-hexanone, 2-decanone,3-methyl-2-pentanone, 4-methyl-2-pentanone,4-methoxy-4-methyl-2-pentanone, cyclopentanone, cyclohexanone,cyclooctanone, 2,6-dimethyl-4-heptanone, 3,5-dimethyl-4-heptanone,2,4-dimethyl-3-pentanone, 1,3-diphenylacetone, 2-octanone, 3-octanone,dihydroisophorone, 4-t-butylcyclohexanone, methylcyclohexyl ketone,acetophenone, 4-piperidone, 2,2,6,6-tetramethyl-4-piperidone and2,6-diethyl-2,3,6-trimethyl-4-piperidone.

Non-limiting examples of suitable aldehydes include formaldehyde,acetaldehyde, butyraldehyde, dodecyl aldehyde, 2-ethylbutyraldehyde,heptaldehye, isobutyraldehyde, isovaleraldehyde, octyl aldehyde,propionaldehyde, valeraldehyde, benzaldehyde,3,5-di-t-butyl-4-hydroxybenzaldehyde, 2,3-dimethyl-p-anisaldehyde,3-hydroxybenzaldehyde, 1-naphthaldehyde, salicylaldehyde, p-tolualdehydeand 2,3,4-trimethoxybenzaldehyde.

Non-limiting examples of suitable isocyanates include allyl, benzyl,n-butyl, sec-butyl, isobutyl, t-butyl, cyclohexyl, ethyl, isopropyl,4-methoxyphenyl, methyl, octadecyl, 1-naphthyl, phenyl, o-, m- andp-tolyl and dimethyl-m-isopropenylbenzyl isocyanates and2-isocyanatoethyl methacrylate.

Non-limiting examples of suitable isothiocyanates include allyl, benzyl,4-bromophenyl, n-butyl, sec-butyl, isobutyl, t-butyl, 3-chlorophenyl,cyclohexyl, ethyl, methyl, propyl, isopropyl, 2-naphthyl, t-octyl,phenethyl, phenyl, propyl, o- and p-tolyl isothiocyanates.

Non-limiting examples of suitable diisocyanates include ethylenediisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylenediisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate,cyclohexane-1,3 and 1,4-diisocyanate and mixtures thereof,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane(isophoronediisocyanate), 2,4- and 2,6-hexahydrotolylene diisocyanate and mixturesthereof, hexahydro-1,3 and/or 1,4-phenylene diisocyanate, perhydro-2,4'and/or 4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylenediisocyanate, 2,4- and 2,6-tolylene diisocyanate and mixtures thereof,diphenylmethane-2,4'- and/or 4,4'-diisocyanate, naphthylene1,5-diisocyanate, m- and p-tetramethylxylene diisocyanate,2,2,4-trimethylhexamethylene diisocyanate and2,4,4-trimethylhexamethylene diisocyanate.

Non-limiting examples of suitable diisothiocyanates include ethylenediisothiocyanate, 1,4-tetramethylene diisothiocyanate, 1,6-hexamethylenediisothiocyanate, 1,4-diisothiocyanatobenzene,1,1'-methylenebis[4-isothiocyanatocyclohexane] and1,1'-oxybis[4-isothiocyanatobenzene].

Non-limiting examples of suitable amic acid esters include methyl,ethyl, propyl, isopropyl, n-butyl and phenyl oxamates and succinamates,ethyl and methyl N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate, ethyl andmethyl N-(2,2,6,6-tetramethyl-4-piperidinyl)succinamate, ethyl andmethyl N-(3,5-di-t-butyl-4-hydroxyphenyl)oxamate and ethyl and methylN-(3,5-di-t-butyl-4-hydroxyphenyl)succinamate.

Non-limiting examples of suitable acid hydrazides include acetyl,propionic, butyric, isobutyric, valeric, isovaleric, caproic, heptanoic,caprylic, decanoic, lauric, myristic, palmitic and stearic hydrazides,benzhydrazide, 3,5-di-t-butyl-4-hydroxybenzhydrazide,3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid hydrazide,3-n-hexylthiopropionic acid hydrazide,(4-benzoyl-3-hydroxyphenoxy)acetyl hydrazide and3-(dimethylaminoethylthio)propionic acid hydrazide.

Non-limiting examples of suitable diacid dihydrazides include succinicacid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide,azelaic acid dihydrazide, dodecanedioic acid dihydrazide and 1,3- and1,4-benzenedicarboxylic acid dihydrazide.

Non-limiting examples of suitable carbazates include ethyl, methyl,propyl, isopropyl, butyl, allyl, methallyl, cyclohexyl, cyclopentyl,cyclododecyl, phenyl, benzyl, 4-t-butylcyclohexyl, 2-ethylhexyl,4-methylphenyl, 3-methoxyphenyl,2-acryloyloxyethyl,2-methacryloyloxyethyl,2-(3-hydroxy-4-benzotriazol-2-ylphenoxy)ethyl,2-(3-hydroxy-4-benzoylphenoxy)ethyl,3-(3,5-di-t-butyl-4-hydroxyphenyl)propyl,2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl,2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl,1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl,2,2,6,6-tetramethyl-4-piperidinyl and1,2,2,6,6-pentamethyl-4-piperidinyl carbazates.

Non-limiting examples of suitable biscarbazates include ethylenebiscarbazate, diethylene glycol biscarbazate, butane-1,4-diylbiscarbazate, butane-1,3-diyl biscarbazate, cycloheptane-1,2-diylbiscarbazate, cyclohexane-1,2-diyl biscarbazate, cyclohexane-1,4-diylbiscarbazate, decane-1,10-diyl biscarbazate, 2,2-diethylpropane-1,3-diylbiscarbazate, 2,2-dimethyl-1,3-diyl biscarbazate, hexane-1,6-diylbiscarbazate and propane-1,3-diyl biscarbazate.

Non-limiting examples of suitable diaryl carbonates include diphenyl,di-4-methylphenyl, di-2-methylphenyl, di-3-methylphenyl,di-3-methoxyphenyl, di-2,6-dimethylphenyl and di-2,5-di-t-butylphenylcarbonates.

Non-limiting examples of suitable sulfonyl hydrazides includebenzenesulfonyl hydrazide, 4-bromobenzenesulfonyl hydrazide,1-butanesulfonyl hydrazide, 4-t-butylbenzenesulfonyl hydrazide,p-toluenesulfonyl hydrazide, ethanesulfonyl hydrazide, methanesulfonylhydrazide, 4-fluorobenzenesulfonyl hydrazide, 1-hexadecanesulfonylhydrazide, isopropanesulfonyl hydrazide and 1-naphthalenesulfonylhydrazide.

Non-limiting examples of suitable bis(sulfonyl hydrazides) include 1,3-and 1,4-benzene bis(sulfonyl hydrazide), 1,2-ethane bis(sulfonylhydrazide), 1,4-butane bis(sulfonyl hydrazide), 1,1'-oxybis(4-benzenesulfonyl hydrazide), 1,1'-methylene bis(4-benzenesulfonylhydrazide) and 1,4-cyclohexane bis(sulfonyl hydrazide).

Non-limiting examples of suitable epoxides include 1,2-epoxybutane,2,3-epoxybutane, 1,2-epoxycyclododecane, 1,2-epoxycyclohexane,1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane,1,2-epoxyoctadecane, 1,2-epoxy-3-phenoxypropane, 2,3-epoxypropylacrylate, 2,3-epoxypropyl methacrylate, 2,3-epoxypropyl-4-methoxyphenylether, glycidyl isopropyl ether, glycidyl n-hexyl ether, glycidyldodecyl ether and glycidyl octadecyl ether.

Non-limiting examples of suitable substituted hydrazines include methyl,ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, amyl, t-amyl,hexyl, heptyl, octyl, 2-ethylhexyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclododecyl, 4-t-butylcyclohexyl,2-methylcyclohexyl, benzyl, alpha-methylbenzyl,alpha,alpha-dimethylbenzyl, phenethyl, phenyl, 2-bromophenyl,2-chlorophenyl, 1,1-dimethyl, 1,2-dimethyl, 1,1-diethyl, 1,2-diethyl,1,1-diphenyl, 3-hydroxybenzyl, 2-hydroxyethyl, 2-methoxyphenyl,4-methoxyphenyl, 1-methyl-1-phenyl, o-, m-, and p-tolyl hydrazines.

UTILITY

The novel stabilizers of the present invention are very effectiveadditives for stabilizing polymeric compositions which are normallysubject to thermal, oxidative or actinic light degradation. At times itmay be beneficial to add extraneous additives which will act assynergists with the hindered amine light stabilizing groups of thepresent invention.

The novel stabilizers of this invention can be blended with variouspolymeric compositions in high concentrations to form masterbatcheswhich can then be blended with additional polypher either of the same ordifferent type.

The amount of stabilizer used to stabilize the polymeric compositionwill depend on the particular polymer system to be stabilized, thedegree of stabilization desired and the presence of other stabilizers inthe composition. Normally it is advisable to have about 0.01% to about5% by weight of the 2,2,6,6-tetraalkylpiperidine moiety of the compoundsof this invention present in the polymeric composition. An advantageousrange is from about 0.05% to about 2% by weight of the2,2,6,6-tetraalkylpiperidine portion of the molecule in the finalcomposition. In most cases, 0.1% to about 1% by weight is sufficient.

Non-limiting examples of polymeric compositions which may be stabilizedby these novel hindered amine light stabilizers include:

(1) Polyolefins such as high, low and linear low density polyethylenes,which may be optionally crosslinked, polypropylene, polyisobutylene,poly(methylbutene-1), polyacetylene and, in general, polyolefins derivedfrom monomers having from 2 to about 10 carbon atoms, and mixturesthereof.

(2) Polyolefins derived from diolefins, such as polybutadiene andpolyisoprene.

(3) Copolymers of monoolefins or diolefins, such as ethylene-propylene,propylene-butene-1, propylene-isobutylene and ethylene-butene-1copolymer.

(4) Terpolymers of ethylene and propylene with dienes (EPDM), such asbutadiene, hexadiene, dicyclopentadiene and ethylidene norbornene.

(5) Copolymers of alpha-olefins with acrylic acid or methacrylic acidsor their derivatives, such as ethylene-acrylic acid,ethylene-methacrylic acid and ethylene-ethyl acrylate copolymers.

(6) Styrenic polymers, such as polystyrene (PS) andpoly(p-methylstyrene).

(7) Styrenic copolymers and terpolymers, such as styrene butadiene(SBR), styrene-allyl alcohol and styrene acrylonitrile (SAN),styrene-acrylonitrile-methacrylate terpolymer, styrene-butadiene-styreneblock copolymers (SBS), rubber modified styrenics such asstyrene-acrylonitrile copolymers modified with acrylic ester polymer(ASA), graft copolymers of styrene on rubbers, such as polybutadiene(HIPS), polyisoprene or styrene-butadiene-styrene block copolymers(Stereon™ products available from Firestone Synthetic Rubber and LatexCo.), graft copolymers of styrene-acrylonitrile on rubbers such asbutadiene (ABS), polyisoprene or styrene-butadiene-styrene blockcopolymers, graft copolymers of styrene-methyl methacrylate on rubbers,such as polybutadiene (MBS), butadiene-styrene radial block copelymers(e.g., KRO 3™ of Phillips Petroleum Co.), selectively hydrogenatedbutadiene-styrene block copolymers (e.g., Kraton G™ from Shell ChemicalCo.) and mixtures thereof.

(8) Polymers and copolymers derived from halogen-containing vinylmonomers, such as poly (vinyl chloride), poly (vinyl fluoride), poly(vinylidene chloride), poly (vinylidene fluoride),poly(tetrafluoroethylene) (PTFE), vinyl chloride-vinyl acetatecopolymers, vinylidene chloride vinyl acetate copolymers and ethylenetetrafluoroethylene copolymers.

(9) Halogenated rubbers, such as chlorinated and/or brominated butylrubbers or polyolefins and fluoroelastomers.

(10) Polyphers and copolymers derived from alpha,beta-unsaturated acids,anhydrides, esters, amides and nitriles or combinations thereof, such aspolymers or copolymers of acrylic and methacrylic acids, alkyl and/orglycidyl acrylates and methacrylates, acrylamide and methacrylamide,acrylonitrile, maleic anhydride, maleimide, the various anhydridecontaining polymers and copolymers described in this paragraph,copolymers of the polymers set forth in this paragraph and variousblends and mixtures thereof, as well as rubber modified versions of thepolymers and copolymers set forth in this paragraph.

(11) Polymers and copolymers derived from unsaturated alcohols or theiracylated derivatives such as poly(vinyl alcohol), poly(vinyl acetate),poly(vinyl stearate), poly(vinyl benzoate), poly(vinyl maleate),poly(vinyl butyral), poly(allyl phthalate), poly(allyldiethylene glycolcarbonate) (ADC), ethylene-vinyl acetate copolymer and ethylenevinylalcohol copolymers.

(12) Polymers and copolymers derived from unsaturated amines such aspoly(allyl melamine).

(13) Polymers and copolymers derived from epoxides, such as polyethyleneoxide, polypropylene oxide and copolymers thereof as well as polymersderived from bis-glycidyl ethers.

(14) Poly(phenylene oxides), poly(phenylene ethers) and modificationsthereof containing grafted polystyrene or rubbers, as well as theirvarious blends with polystyrene, rubber modified polystyrenes or nylon.

(15) Polycarbonates and especially the aromatic polycarbonates, such asthose derived from phosgene and bisphenols such as bisphenol-A,tetrabromobisphenol-A and tetramethylbisphenol-A.

(16) Polyesters derived from dicarboxylic acids and diols and/orhydroxycarboxylic acids or their corresponding lactones, such aspolyalkylene phthalates (e.g., polyethylene terephthalate (PET),polybutylene terephthalate (PBT), and poly (1,4-dimethylcyclohexaneterephthalate), or copolymers thereof and polylactones such aspolycaprolactone.

(17) Polyarylates derived from bisphenols (e.g., bisphenol-A) andvarious aromatic acids, such as isophthalic and terephthalic acids ormixtures thereof.

(18) Aromatic copolyester carbonates having carbonate, as well as esterlinkages present in the backbone of the polymers, such as those derivedfrom bisphenols, iso- and terephthaloyl chlorides and phosgene.

(19) Polyurethanes and polyureas.

(20) Polyacetals, such as polyoxymethylenes and polyoxymethylenes whichcontain ethylene oxide as a comonomer.

(21) Polysulfones, polyethersulfones and polyimidesulfones.

(22) Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactones, such as the following nylons: 6, 6/6, 6/10, 11and 12.

(23) Polyimides, polyetherimides, polyamideimides and copolyetheresters.

(24) Cross-linked polymers which are derived from aldehydes on the onehand and from phenols, ureas and melamine on the other hand, such asphenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

(25) Alkyl resins, such as glycerolphthalic acid resins and mixturesthereof with melamine-formaldehyde resins.

(26) Blends of vinyl monomers and unsaturated polyester resins which arederived from copolyesters of saturated and unsaturated dicarboxylicacids with polyhydric alcohols, as well as from vinyl compounds(crosslinking agents) and also halogen-containing, flame resistantmodifications thereof.

(27) Natural polymers, such as cellulose and natural rubber, as well asthe chemically modified homologous derivatives thereof, such ascellulose acetates, cellulose propionate, cellulose butyrate and thecellulose ethers such as methyl and ethyl cellulose.

In addition, the novel stabilizers of this invention may be used tostabilize various combinations or blends of the above polymers orcopolymers. They are particularly useful in the stabilization ofpolyolefins, acrylic coatings, styrenics, rubber modified styrenics,poly(phenylene oxides) and their various blends with styrenics, rubbermodified styrenics or nylon.

The novel hindered amine light stabilizers of this invention can be usedtogether with other additives to further enhance the properties of thefinished polymer. Examples of other additives that can be used inconjunction with the stabilizers of this invention include antioxidants,such as alkylated monophenols, alkylated hydroquinones, hydroxylatedthiodiphenyl ethers, alkylidene-bisphenols, hindered phenolic benzylcompounds, acylaminophenols, esters of3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid, esters of3-(5-t-butyl-4-hydroxy-3-methylphenyl)propionic acid,3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid amides; UV absorbersand light stabilizers such as 2-(2'-hydroxyphenyl)-2H-benzotriazoles,2-hydroxy benzophenones, benzylidene malonate esters, esters ofsubstituted or unsubstituted benzoic acids, diphenyl acrylates, nickelchelates, oxalic acid diamides, other hindered amine light stabilizers,other additives such as metal deactivators, phosphites and phosphonites,peroxide decomposers, fillers and reinforcing agents, plasticizers,lubricants, corrosion and rust inhibitors, emulsifiers, mold releaseagents, carbon black, pigments, fluorescent brighteners, both organicand inorganic flame retardants and non-dripping agents, melt flowimprovers and antistatic agents. Numerous examples of suitable additivesof the above type are given in Canadian Patent 1,190,038.

A presently preferred additive is 2,4-di-t-butylphenyl3,5-di-t-butyl-4-hydroxybenzoate preferably added in an amount of about0.01% to about 1.0% by weight of the composition to which it is added.

The following examples are presented to provide a more detailedexplanation of the present invention and are intended as illustrationsand not limitations of the invention.

EXAMPLES Starting Materials

Ethyl N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate was prepared byreacting 4-amino-2,2,6,6-tetramethylpiperidine with an excess of diethyloxalate and subsequently stripping off the excess diethyl oxalate.

Methyl N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate was formed by esterexchange wherein the above ethyl ester was dissolved in methanol andallowed to stand at room temperature for a minimum of 24 hours.

HALS-O

N-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminooxamide was prepared bythe hydrazinolysis of methyl or ethylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate with 85% hydrazine hydratein methanol.

HALS-2

N-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminosuccinamide was preparedby the reaction of 4-amino-2,2,6,6-tetramethylpiperidine with ethylsuccinyl chloride followed by hydrazinolysis of the resulting ester with85% hydrazine hydrate in methanol.

HALS-4

N-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminoadipamide was prepared byreacting 4-amino-2,2,6,6-tetramethylpiperidine with ethyl adipoylchloride, followed by hydrazinolysis of the resulting ester with 85%hydrazine hydrate in methanol.

HALS-5

4-Hydrazinocarbonyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)-2-pyrrolidonewas prepared by the hydrazinolysis of4-(methoxycarbonyl)-1-(2,2,6,6-tetramethyl-4-piperidinyl)-2-pyrrolidonewith excess hydrazine hydrate in methanol. The above intermediate halfester was prepared by the addition of4-amino-2,2,6,6-tetramethylpiperidine to dimethyl itaconate according tothe procedure described in U.S. Pat. No. 4,309,546.

3-(3,5-Di-t-butyl-4-hydroxyphenyl)propionhydrazide was prepared by thehydrazinolysis of ethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate inmethanol.

3,5-Di-t-butyl-4-hydroxybenzhydrazide was prepared by the hydrazinolysisof 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate (UV Chek AM340--a product of Ferro Corp.) in methanol.

N-(3,5-di-t-butyl-4-hydroxyphenyl)-N'-aminooxamide was prepared byreacting 3,5-di-t-butyl-4-hydroxyaniline with ethyl oxalyl chloridefollowed by hydrazinolysis of the resulting ester with 85% hydrazinehydrate in methanol.

(4-Benzoyl-3-hydroxyphenoxy)acetylhydrazide was prepared by reacting2,4-dihydroxybenzophenone with ethyl chloroacetate in the presence ofpotassium carbonate. The resulting ester was converted to the hydrazideby hydrazinolysis with 85% hydrazine hydrate in methanol.

m-Tetramethylxylene diisocyanate (TMXDI) andm-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate (TMI) were obtainedfrom American Cyanamid Company.

Isophorone diisocyanate was obtained from Nuodex, a division of HulsAmerica, Inc.

Irganox™ 1076 [octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],Tinuvin™ 770 (di-2,2,6,6-tetramethyl-4-piperidinyl sebacate) andChimasorb™ 944[(N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexane-diamine,polymer with 2,4,6-trichloro-1,3,5-triazine and2,4,4-trimethyl-1,2-pentanamine] were obtained from Ciba GeigyCorporation.

UV-Chek™ AM-340 (2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate)was obtained from the Chemical Division of Ferro Corporation.

Benzenesulfonyl hydrazide was obtained from Canada Colors and ChemicalsLimited.

Butyric, isobutyric, valerie, caproic, heptanoic, caprylic, decanoic,lauric, myristic and stearic hydrazides were prepared by thehydrazinolysis of the corresponding methyl esters with hydrazinehydrate. The methyl esters were purchased from Aldrich Chemical Co.

n-Butyl isocyanate, 1,6-hexamethylene diisocyanate, octadecylisocyanate, phenyl isocyanate, tolylene 2,4-diisocyanate, n-butylisothiocyanate, cyclohexanone, ethyl carbazate, 2-ethylhexyl glycidylether, 1,2-epoxy-3-phenoxypropane, methylhydrazine,3,5-di-t-butyl-4-hydroxybenzaldehyde, acetic hydrazide, adipicdihydrazide, benzoic hydrazide, salicylic hydrazide, propionic, butyric,valerie, hexanoic and heptanoic anhydrides and2,2,6,6-tetramethyl-4-piperidone hydrochloride were purchased fromAldrich Chemical Company, Inc.

EXAMPLE I Preparation of the n-Butyl Isothiocyanate Adduct ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminooxamide ##STR28##

To a slurry of N-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminooxamide(12.2 g, 0.05 mole) (HALS-O) in 200 mls of tetrahydrofuran (THF) wasadded dropwise n-butyl isothiocyanate (5.8 g, 0.05 mole) over severalminutes. There was no observable exotherm. The reaction was stirred 1/2hour at room temperature and then heated to reflux for 45 minutes. Ahomogeneous solution was obtained when the reaction temperature reached50° C. After cooling to room temperature, the reaction mixture wasfiltered. The filter cake was air dried overnight and weighed 16.6grams. The product melted from 170°-181° C. A liquid chromatography scanshowed the presence of only one component. An infrared (IR) scan (nujolmull) contained strong sharp carbonyl bands at 1668 and 1604 cm⁻¹. TheIR scan was consistent with the structure of the desired product.

EXAMPLES II-XIV Preparation of Isocyanate and Diisocyanate Adducts ofN-(2,2,6,6-tetramethyl-4-piperidinyl)amic Acid Hydrazides ##STR29##

The isocyanate and diisocyanate adducts were prepared by adding equalequivalents of the isocyanate or diisocyanate indicated in Table I to astirring slurry of the N-(2,2,6,6-tetramethyl-4-piperidinyl)amic acidhydrazide in THF. The addition was typically started at room temperatureand the temperature was allowed to rise throughout the addition (5-10minutes). The reaction was stirred an additional hour, after which thereaction was usually complete. To assure complete reaction of theisocyanate, the reaction mixtures were heated to reflux and refluxed 1to 21/2 hours in some examples. If the product was insoluble in THF, itwas isolated by filtration and air dried. If the product was soluble inTHF, it was isolated by evaporating the solvent on a rotating evaporatorunder reduced pressure. The residue was pulverized with a mortar andpestle and air dried overnight.

The products were characterized by their melting ranges and infraredspectra. The infrared spectra were run in solution or as nujol mulls.

Example IX was prepared using methyl ethyl ketone as the solvent insteadof THF.

Information including reactants, reaction parameters, structures ofproducts and results are summarized in Table I.

    TABLE I      ISOCYANATE AND DIISOCYANATE ADDUCTS OF HALS AMIC ACID HYDRAZIDES      ##STR30##       EX-         REAC-  ISOLA-    AM-     HALS    TION RE- TION  MELTING     PLE     HYDRA-  ISOCYANATES OR  TEMP, FLUX METH- YIELD RANGE INFRARED     CARBONYL # m R.sup.15 R.sup.2 R.sup.3 ZIDE GRAMS DIISOCYANATES GRAMS     °C. TIME OD (GRAMS) °C. BANDS cm.sup.-1       II 1 C.sub.6 H.sub.5 H DIRECT HALS-0 24.8 PHENYL 11.9 20-37 -- FILT.     39.7 213- 218 1670,1590,1550(NUJOL)     BOND   ISOCYANATE III 1 n-C.sub.4      H.sub.9 H DIRECT HALS-0 24.8 n-BUTYL 9.9 19-28 21/2 hrs FILT. 34.2     159-161 1655,1620,1500(NUJOL)     BOND   ISOCYANATE IV 1 C.sub.18     H.sub.37 H DIRECT HALS-0 12.4 OCTADECYL 14.8 22-35 -- EVAP. 24.6 92-94     1660,1590,1500(CHCl.sub.3)     BOND   ISOCYANATE V 1 n-C.sub.4 H.sub.9 H (     CH.sub.2).sub.2 HALS-2 6.75 n-BUTYL 2.5 22-25 21/2 hrs EVAP. 8.2     1655,1540 (CHCl.sub.3)        ISOCYANATE VI 1 n-C.sub.4 H.sub.9 H     CH.sub.2).sub.4 HALS-4 6.7 n-BUTYL 2.2 22-25 11/2 hrs EVAP. 8.4     1635,1540 (CHCl.sub.3)        ISOCYANATE  VII 1 n-C.sub.4 H.sub.9      ##STR31##      HALS-5 7.1 n-BUTYLISOCYANATE 2.5 22-27 1 hr FILT. 7.1 179-182 1655,1545     (NUJOL)  VIII 1 C.sub.18 H.sub.37  " HALS-5 7.1 OCTADECYL 7.4 22-27 1 hr     EVAP. 12.8 68-70 1655,1550 (NUJOL)        ISOCYANATE      IX 2     ##STR32##      H DIRECTBOND HALS-0 14.8 TOLYLENE 2,4-DIISOCYANATE 5.2 22-25 -- FILT.     20.0 183-185 1650,1590,1510(NUJOL)      X 2     ##STR33##      H DIRECTBOND HALS-0 24.8 ISOPHORONEDIISOCYANATE 11.1 23-37 1 hr FILT.     35.7 185-195 1645,1580,1500(NUJOL)      XI 2     ##STR34##      H DIRECTBOND HALS-0 18.2 TMXD 9.15 45-49 -- FILT. 27.3 202-205 1665,1600     ,1570(NUJOL)      XII 2 (CH.sub.2).sub.6 H DIRECT HALS-0 24.8 1,6-HEXAMETHYLENE 8.6 23-28     2 hrs FILT. 31.8 163-167 1655,1590,1500(NUJOL)     BOND   DIISOCYANATE     XIII 2      ##STR35##      ##STR36##      HALS-5 8.5 ISOPHORONEDIISOCYANATE 3.35 22-29 1 hr EVAP. 11.3 210-215     1670,1545 (NUJOL)      XIV 2 (CH.sub.2).sub.6 H     ##STR37##      HALS-5 14.1 1,6-HEXAMETHYLENEDIISOCYANATE 4.2 23-31 1 hr EVAP. 18.7     146-160 1660,1550,1490(CHCl.sub.3)

EXAMPLES XV-XX Hydrazone Derivatives ofN-(2,2,6,6-tetramethyl-4-piperidinyl)amic Acid Hydrazides ##STR38##

The hydrazone derivatives indicated in Table II were prepared byreacting equal equivalents (or a slight excess of ketone) of the HALShydrazide with the ketone in toluene or xylene and azeotropicallydistilling off the water formed in the reaction. The reactions wererefluxed using a reflux condenser connected to a Dean Stark trap, untilwater no longer formed in the trap. Insoluble products were isolated byfiltration and soluble products were isolated by solvent evaporation ona rotating evaporator under reduced pressure. Product residues weregenerally pulverized, rinsed with a non-solvent or poor solvent toremove any residual starting material and air dried overnight.

The products were characterized by their melting ranges and infraredspectra. The infrared spectra were run in solution or as nujol mulls.

In Example XVIII, the free base of the 2,2,6,6-tetramethyl-4-piperidonehydrochloride salt (obtained from the Aldrich Chemical Co.) wasliberated with aqueous caustic prior to running the reaction. The waterfrom the caustic and the water generated by the reaction were removed byazeotropic distillation.

Information including reactants, reaction parameters, structures ofproducts and the results are summarized in Table II.

    TABLE II      HYDRAZONE DERIVATIVES OF HALS AMIC ACID HYDRAZIDES      ##STR39##       EX-    HALS      ISOLA-     AM-    HY-     AZEO- TION   MELTING     INFRARED PLE    DRA-  ALDEHYDE   TROPE METH- WASH YIELD RANGE CARBONYL #     R.sup.2 R.sup.3 C(R.sup.11)(R.sup.12) ZIDE GRAMS OR KETONE GRAMS SOLVENT     PERIOD OD SOLVENT (GRAMS) °C. BANDS cm.sup.-1       XV H DIRECT C(CH.sub.3).sub.2 HALS-0 24.2 ACETONE 8.2 TOLUENE 16 hrs.     EVAP. HEXANE 26.3 122- 124 1645,1495   BOND            (XYLENE) XVI H     DIRECT C(CH.sub.3)(C.sub.2 H.sub.5) HALS-0 24.2 METHYL ETHYL 8.0 XYLENE     10 hrs. EVAP. -- 27.1  1645,1495   BOND    KETONE        (XYLENE) XVII H D     IRECTBOND      ##STR40##      HALS-0 24.2 CYCLOHEXANONE 9.8 XYLENE 21/2 hrs. EVAP. METHYLt-BUTYLETHER     22.0 130-133 1655,1530(NEAT)1655,1545,1500(NUJOL)  XVIII H DIRECTBOND      ##STR41##      HALS-0 12.7 2,2,6,6-TETRAMETHYL-4-PIPERIDONE 7.8 TOLUENE 12 hrs. FILT.     -- 9.6 203-205 1670,1490(CHCl.sub.3)      XIX H DIRECTBOND     ##STR42##      HALS-0 12.7 2,5-Di-t-BUTYL-4- HYDROXY-BENZALDEHYDE 11.8 XYLENE 2 hrs     FILT. HEXANE 19.9 142-150 1645,15901520(NUJOL)      XX     ##STR43##      C(CH.sub.3)(C.sub.2 H.sub.5) HALS-5 14.1 METHYL ETHYLKETONE 7.2 XYLENE     61/2      hrs. EVAP. TETRA-HYDRO-FURAN 11.8 126-130 1675,1490(NUJOL)

EXAMPLE XXI Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-dodecanoylhydrazine##STR44##

Into a 3-necked 300 ml flask was introduced a 60.9% solution of ethylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate in methanol (21.0 g, 0.05mole), lauric acid hydrazide (13.5 g) and 150 ml of anhydrous methanol.The flask was equipped with a thermometer, a magnetic stirrer and a DeanStark trap with a reflux condenser. The reaction mixture was heated toreflux and the methanol was slowly distilled off through the Dean Starktrap. The disappearance of the starting materials and the formation ofthe products were monitored by liquid chromatography. After 6 hours atreflux and the removal of 110 ml of methanol, the liquid chromatographscans indicated the reaction was essentially complete. The reactionmixture was filtered hot and the filtrate was stripped to dryness on arotating evaporator under reduced pressure. The residue was a whitepowder weighing 16.6 g and had a melting range of 80°-84° C. An infraredscan (nujol mull) of the product contained strong carbonyl bands at1655, 1580 and 1490 cm⁻¹.

A second crop of 2.35 g of product (melting range 88°-92° C.) wasobtained by dissolving the filter cake in methanol, filtering off asmall amount of insoluble material and stripping the filtrate todryness.

EXAMPLE XXII Preparation of1-[N-(2,2,6,6-tetramethyl-4piperidinyl)oxamoyl]-2-ethoxycarbonylhydrazine##STR45##

Into a 3-necked 250 ml flask was introduced a 60.9% solution of ethylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate in methanol (21.0 g, 0.05mole), ethyl carbazate (5.2 g, 0.05 mole) and 100 ml of anhydrousmethanol. The flask was equipped with a thermometer, a magnetic stirrerand a Dean Stark trap with a reflux condenser. The reaction mixture washeated to reflux and the methanol was slowly distilled off through theDean Stark trap. After 5 hours at reflux and the removal of 75 ml ofmethanol, the reaction mixture partially solidified. The reactionmixture was diluted with 15 ml of methanol and filtered hot. Thefiltrate was stripped to dryness on a rotating evaporator under reducedpressure. The residue was a white powder weighing 8.4 g and had amelting range of 106°-109° C. A liquid chromatographic scan indicatedthe presence of one component. An infrared scan (nujol mull) of theproduct contained strong carbonyl bands at 1685 cm⁻¹ and 1590 cm⁻¹ andweak carbonyl bands at 1530 cm⁻¹ and 1485 cm⁻¹.

A second crop of 3.45 g of product (melting range 97°-100° C.) wasobtained by dissolving the filter cake in methanol, filtering off asmall amount of insoluble material and stripping the filtrate todryness.

1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-ethoxycarbonylhydrazinewas also prepared in 75% yield by reacting equivalent amounts of4-amino-2,2,6,6-tetramethylpiperidine and1-ethoxalyl-2-ethoxycarbonylhydrazine (prepared from ethyl carbazate andethyl oxalyl chloride) in methanol.

EXAMPLE XXIII Preparation of1,2-Di-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]hydrazine ##STR46##

Into a 3 liter 3-necked flask was introducedN-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminooxamide (HALS-O) (165 g,0.68 mole) and 1600 ml methanol. The flask was equipped with a magneticstirrer, a thermometer and a Dean Stark trap with a reflux condenser.The mixture was heated in an oil bath and upon warming to 50° C., theHALS-O was completely dissolved. To the warm solution was added a 60.9%solution of ethyl N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate (271 g,0.644 mole). The solution was added dropwise over 15 minutes from adropping funnel inserted in the center neck of the flask. The reactionmixture was still a clear solution at the end of the addition but uponheating to reflux, solid material began to form. The reaction mixturewas refluxed for 4 hours while slowly removing about 750 ml of methanolby periodically draining the Dean Stark trap. At the end of the reluxperiod, the 750 ml of methanol was added back to the reaction flask andthe mixture was cooled to 50° C. and filtered. The filter cake wasfiltered semi-dry, washed with fresh methanol, pulled semi-dry and airdried on drying paper overnight. The product weighed 195 g and had amelting range of 298°-303° C.

A second crop of 31.5 g of product was obtained by cooling the methanolfiltrate and refiltering it.

The infrared scan of the product contained strong, sharp carbonyl bandsat 1655, 1580 and 1495 cm⁻¹.

EXAMPLE XXIV Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine##STR47##

Into a 3-necked 100 ml flask was introduced methylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate (4.85 g, 0.02 mole) and 50ml of methanol. The flask was equipped with a magnetic stirrer, athermometer and a reflux condenser. The mixture was stirred until all ofthe solid material dissolved, following which3-(3,5-di-t-butyl-4-hydroxyphenyl)propionhydrazide (5.85 g, 0.02 mole)was added and the mixture was refluxed for 2 hours. The solid materialwas filtered off and air dried. The product weighed 2.7 g and had amelting range of 255°-257° C. The infrared scan of the product containedstrong carbonyl bands at 1655, 1620, 1590 and 1490 cm⁻¹.

A second crop of 2.5 g of product was obtained by concentrating thefiltrate at the reflux temperature until solid material formed. Themixture was cooled, re-filtered and the isolated solid was air dried.

EXAMPLE XXV Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[(3,5-di-t-butyl-4-hydroxy)benzoyl]hydrazine##STR48##

Into a 3-necked flask was introduced a 58% solution of methylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate in methanol (20.8 g, 0.05mole) and 200 ml of additional anhydrous methanol. The flask wasequipped with a magnetic stirrer, a thermometer and a Dean Stark trapwith a relux condenser. The mixture was stirred and3,5-di-t-butyl-4-hydroxybenzhydrazide (13.3 g, 0.05 mole) was added overabout 5 minutes. A homogeneous solution was obtained. The reaction washeated to reflux in an oil bath and refluxed for 21/2 hours. Themethanol was then slowly distilled off by periodically draining the DeanStark trap until solid material began to form. Approximately 50 ml ofmethanol was removed over 21/2 hours. The reaction was cooled to roomtemperature and the solid material was filtered off and air dried. Theproduct weighed 10.7 g and had a melting range of 178°-182° C.

An additional 10.3 g of product was obtained by concentrating thefiltrate and refiltering. Both crops were combined, slurried in 125 mlof acetone, filtered and air dried. The product was a white powder whichturned a light yellow color upon exposure to air. The combined productweighed 20.4 g and had a melting range of 184°-189° C. The infrared scan(nujol mull) of the product contained carbonyl peaks at 1635, 1590 and1555 cm⁻¹.

EXAMPLE XXVI Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-stearoylhydrazine##STR49##

Into a 3-necked 500 ml flask was added a 55% solution of ethylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate (20.4 g, 0.044 mole) inanhydrous methanol and 300 ml of additional methanol. The flask wasequipped with a magnetic stirrer, a thermometer and a Dean Stark trapwith a reflux condenser. The mixture was stirred and stearic acidhydrazide (14.95 g, 0.05 mole) was added. The reaction was heated in anoil bath to reflux. The reaction was refluxed for 6 hours and 180 ml ofmethanol was distilled off by periodically draining the Dean Stark trapduring the last hour. The hot reaction mixture was filtered to remove asmall amount of unknown insoluble material. The solution was cooled toroom temperature and was re-filtered to remove 1.1 g of stearic acidhydrazide. The filtrate was stripped to dryness on a rotating evaporatorunder reduced pressure. The residue was scraped out of the flask andpulverized into a white powder with a mortar and pestle. The productweighed 20.2 g and had a melting range of 78°-82° C. The infrared scan(nujol mull) of the product contained broad carbonyl bands at 1655, 1585and 1495 cm⁻¹.

1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-stearoylhydrazine wasalso prepared in 64% yield by reacting equivalent amounts of4-amino-2,2,6,6-tetramethylpiperidine and1-ethoxalyl-2-stearoylhydrazine (prepared from reacting stearic acidhydrazide with ethyl oxalyl chloride) in methanol.

EXAMPLE XXVII Alkylation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminooxamide with 2-EthylhexylGlycidyl Ether ##STR50## where R' is hydrogen, a or b;

R" is hydrogen, a or b;

R'" is hydrogen, a or b; ##STR51##

Into a 50 ml 3-necked flask was introducedN-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminooxamide (HALS-O) (6.1 g,0.025 mole) and 2-ethylhexyl glycidyl ether (4.65 g, 0.025 mole). Theflask was equipped with a magnetic stirrer, a thermometer and a refluxcondenser. The flask was placed in an oil bath and heated to 150°-160°C. for 1 hour with stirring. The reaction mixture was cooled to 130° C.and poured into a small beaker. The viscous liquid was cooled to abrittle solid over dry ice and pulverized with a mortar and pestle. Uponwarming to room temperature it became a viscous liquid again. The liquidchromatographic scan of the product showed a large peak for the startingHALS-O and two major peaks for the monoalkylated (i.e., where R' and R"are hydrogen and R'" is a or b) and dialkylated (i.e., where R' ishydrogen and R" and R'" are a or b) products. There was no residual2-ethylhexyl glycidyl ether. The reaction with HALS-O (3.05 g, 0.0125mole) and 2-ethylhexyl glycidyl ether (4.65 g, 0.025 mole) was repeated.The reaction mixture was heated for 1 hour at 145°-160° C., followed bycooling to room temperature.

The product was a viscous liquid containing five components by liquidchromatography: three major components and small amounts of residualHALS-O and 2-ethylhexyl glycidyl ether. Of the three major components,the retention time of the smaller component corresponded to themonoalkylated product. The largest peak corresponded to the retentiontime of the dialkylated product and a new peak having the shortestretention time corresponded to a trialkylated product (i.e., where R',R" and R'" are a or b).

The reaction with HALS-O (3.05 g, 0.0125 mole) and 2-ethylhexyl glycidylether (7.0 g, 0.0375 mole) was again repeated. The reaction mixture washeated for 4 hours at 140°-150° C. and was monitored by liquidchromatography. After heating for 1 hour, the reaction mixture containedlarge amounts of 2-ethylhexyl glycidyl ether and monoalkylated product,a moderate amount of dialkylated product, a small amount of HALS-O and atrace amount of the trialkylated product. After heating for 2 hours,there were still large, roughly equal amounts of the dialkylated andtrialkylated products, moderate amounts of residual epoxide andmonoalkylated product and a trace amount of residual HALS-O. After 4hours heating, the major product was the trialkylated product with onlysmall traces of the mono and dialkylated products. The reaction wascooled to room temperature, leaving a viscouus liquid as the product.

EXAMPLE XXVIII Alkylation of N-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminooxamide with 1,2-epoxy-3-phenoxypropane##STR52##

Into a 50 ml 3-necked flask was introducedN-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminooxamide (HALS-O) (6.1 g,0.025 mole) and 1,2-epoxy-3-phenoxypropane (11.3 g, 0.075 mole). Theflask was equipped with a magnetic stirrer, a thermometer and a refluxcondenser. The flask was then placed in an oil bath and heated to 150°C. for 3 hours. Liquid chromatography of the reaction mixture indicatedthat primarily the trialkylated product was present, with small amountsof the mono and dialkylated HALS-O and epoxide remaining. The productwas cooled to room temperature and was a very viscous liquid.

EXAMPLE XXIX Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[N-(2,2,6,6-tetramethyl-4-piperidinyl)succinamoyl]hydrazine##STR53##

Into a 3-necked 50 ml flask was introduced a 60.9% solution of ethylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate in methanol (4.27 g, 0.01mole), N-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminosuccinamide (2.7 g,0.01 mole) and 25 ml of anhydrous methanol. The flask was equipped witha thermometer, a magnetic stirrer and a Dean Stark trap with a refluxcondenser. The reaction mixture was heated to reflux for 1/2 hour.Liquid chromatography of the reaction mixture indicated that thestarting materials had essentially disappeared and there was one newpeak corresponding to the product. The reaction mixture was filtered hotto remove some insoluble material. The filtrate was stripped to drynesson a rotatary evaporator under reduced pressure. The residue was scrapedout of the flask and pulverized into a white powder with a mortar andpestle. The white powder was air dried on a watch glass overnight. Theproduct weighed 1.0 grams and had a melting range of 130°-135° C. Aninfrared scan (nujol mull) of the product contained a strong carbonylband at 1655 cm⁻¹ and two moderate carbonyl bands at 1575 and 1495 cm⁻¹.

EXAMPLE XXX Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[N-(3,5-di-t-butyl-4-hydroxyphenyl)oxamoyl]hydrazine##STR54##

Into a 3-necked 300 ml flask was introduced a 58% solution of methylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate in methanol (8.3 g, 0.02mole), N-(3,5-di-t-butyl-4-hydroxyphenyl)-N'-aminooxamide (6.1 g, 0.02mole) and 100 ml of anhydrous methanol. The flask was equipped with amagnetic stirrer, a thermometer and a Dean Stark trap containing areflux condenser. The reaction mixture was heated in an oil bath toreflux for 31/2 hours. At this point, the Dean Stark trap wasperiodically drained until 40 ml of methanol was collected and solidmaterial formed in the reaction mixture. An additional 10 ml of methanolwas distilled from the reaction mixture. The reaction mixture was cooledto 15° C. and the resulting thick slurry was filtered. The filter cakewas rinsed with 20 ml of cold methanol and air dried. The product was awhite solid weighing 6.2 grams and had a melting range of 196°-202° C.The infrared scan (nujol mull) contained sharp carbonyl bands at 1665,1585 and 1510 cm⁻¹.

EXAMPLE XXXI Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxanoyl]-2-[(4-benzoyl-3-hydroxyphenoxy)acetyl]hydrazine##STR55##

Into a 3-necked 500 ml flask was introduced a 58% solution of methylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate in methanol (21.0 g, 0.05mole), (4-benzoyl-3-hydroxyphenoxy)acetyl hydrazide (14.25 g, 0.05 mole)and 200 ml of anhydrous methanol. The flask was equipped with a magneticstirrer, a thermometer and a Dean Stark trap containing a refluxcondenser. The reaction mixture was heated in an oil bath to reflux for3 hours. At this point, the Dean Stark trap was periodically drained toremove a total of 100 ml of methanol. The reaction mixture was cooled to30° C. and filtered. The filter cake weighed 10.4 grams, had a meltingrange of 191°-195° C. and was identified as the starting(4-benzoyl-3-hydroxyphenoxy)acetyl hydrazide. The yellow filtrate wasstripped on a rotatary evaporator yielding 7.3 g of a cream-coloredsolid which did not melt below 280° C. The infrared scan (nujol mull) ofthe high melting solid contained strong sharp carbonyl bands at 1665,1625, and 1505 cm⁻¹ and a weak shoulder at 1595 cm⁻¹.

EXAMPLE XXXII Preparation of 1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-benzenesulfonylhydrazine ##STR56##

Into a 3-necked 250 ml flask was introduced a 60.9% solution of ethylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate in methanol (21.0 g, 0.05mole), benzenesulfonyl hydrazide (8.6 g, 0.05 mole) and 125 ml ofanhydrous methanol. The flask was equipped with a thermometer, amagnetic stirrer and a Dean Stark trap with a reflux condenser. Themixture was stirred to dissolve the benzenesulfonyl hydrazide and wasthen heated to reflux for 11/2 hours. Methanol was slowly distilled off(approximately 100 ml total) until solid material began to form.

The reaction mixture was filtered to remove the insoluble material. Aliquid chromatographic scan of the filtrate indicated that the startingmaterials were essentially consumed and a new product had formed. Thefiltrate was stripped to dryness leaving a white residue weighing 9.7 g.The product had a melting range of 88°-92° C. An infrared scan of theproduct (in CHCl₃) contained strong, broad carbonyl bands at 1670 cm⁻¹and 1500 cm⁻¹ and a weak carbonyl band at 1610 cm⁻¹.

EXAMPLE XXXIII Preparation ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-N-'-methylaminooxamide ##STR57##Method A

Into a 3-necked 250 ml flask was introduced methylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate (12.1 g, 0.05 mole),dissolved in 100 ml of methanol. The flask was equipped with athermometer, a magnetic stirrer, a reflux condenser and a droppingfunnel containing methylhydrazine (2.8 g, 0.06 mole). Themethylhydrazine was added dropwise to the stirring oxamate solution atroom temperature. The reaction was stirred for 5 hours at roomtemperature and was then allowed to stand overnight. The solvent wasstripped off the next morning on a rotatary evaporator under reducedpressure. The residue was a white solid weighing 12.5 g with a meltingrange of 164°-168° C.

The infrared spectrum of the product contained a strong carbonyl at 1640cm⁻¹ and a moderate carbonyl band at 1520 cm⁻¹. The ester band at 1730cm⁻¹ corresponding to the starting material was not present.

Method B

Monoethyl oxalyl-2-methylhydrazide was prepared by adding an equivalentamount of methylhydrazine to a methanol solution of diethyl oxalate at15°-20° C. The insoluble material that formed was filtered off and theproduct was isolated by removing the methanol from the filtrate on arotatary evaporator under reduced pressure.

To a solution of the monoethyl oxalyl-2-methylhydrazide (3.7 g, 0.025mole) in 20 ml of methanol in a 50 ml flask was added4-amino-2,2,6,6-tetramethylpiperidine (4.2 g). The reaction was stirredat room temperature for 1 hour and then refluxed for 1 hour.

Upon cooling, the product crystallized out of solution. The product wasisolated by filtration and air dried. The yield of isolated product was2.85 grams (44.5% yield). The infrared scan of the product was the sameas that of the product prepared fromN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate and methylhydrazine.

EXAMPLE XXXIV Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-acetylhydrazine##STR58## Method A

Into a 3-necked 100 ml flask was introduced acetic hydrazide (3.75 g,0.05 mole) and a 60% solution of methylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate in anhydrous methanol (20.7g, 0.05 mole). The flask was equipped with a magnetic stirrer, athermometer and a Dean Stark trap equipped with a reflux condenser. Theflask was placed in an oil bath and the reaction mixture was heated toreflux. Upon reaching reflux temperature (about 70° C.), a white solidquickly formed and a thick slurry resulted within 5 minutes. The slurrywas refluxed for 1/2 hour at 70°-73° C. and was then diluted with 50 mlof methanol. The slurry was filtered hot (60° C.) and the filter cakewas rinsed with 25 ml of fresh methanol. After air drying overnight on awatch glass, the white powder weighed 8.6 g (60.5% yield). The producthad a melting point of 267°-269° C. An infrared scan (nujol mull) of theproduct contained carbonyl bands at 1660, 1620, 1565 and 1510 cm⁻¹.

Additional product (5.4 g, 38% yield) was recovered by distilling offmost of the methanol from the filtrate and refluxing the residue (72°C.) for 10 minutes and repeating the recovery procedure with 25 ml ofmethanol.

Method B

Into a 3-necked flask was introduced 98%N-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-aminooxamide (HALS-O) (12.4 g,0.05 mole) and 125 ml of THF. The flask was equipped with a magneticstirrer, a thermometer, a reflux condenser and a dropping funnelcontaining acetic anhydride (5.1 g, 0.05 mole) diluted to 25 ml withTHF. The stirrer was activated and the anhydride solution was addeddropwise to the stirring slurry of HALS-O over 2-3 minutes. The reactiontemperature rose from 22° C. to 32° C. and the slurry changed inphysical appearance. After the addition was complete, the reaction wasstirred 1 hour while the temperature dropped back to 26° C. The slurrywas filtered and the filter cake was slurried in 100 ml of 3% sodiumbicarbonate solution and refiltered. The filter cake was air driedovernight on a watch glass. After drying, the product weighed 12.6 g(88.7% yield). The product had a melting point of 265°-268° C. and theinfrared scan (nujol mull) of the product was the same as that of theproduct from Method A.

EXAMPLE XXXV Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-propionylhydrazine##STR59##

Into a 3-necked 250 ml flask was introduced HALS-O (12.2 g, 0.05 mole)and 150 ml THF. The flask was equipped with a magnetic stirrer, athermometer, a reflux condenser and a dropping funnel containingpropionic anhydride (6.5 g, 0.05 mole) diluted to 15 ml with THF. Thestirrer was activated and the propionic anhydride solution was addeddropwise over 5 minutes. The reaction temperature slowly rose from 19°C. to 27° C. where the reaction mixture gelled. The reaction mixture washeated to reflux in an oil bath for 1 hour. The gelled material wentinto solution upon heating followed by a solid material precipitatingout of solution to form a thin slurry. The reaction was cooled to 50° C.and filtered. The filter cake was washed with fresh THF and then airdried overnight. The product was a white powder weighing 13.9 g (93%yield). The product had a melting range of 221°-225° C. and the infraredscan (nujol mull) of the product contained carbonyl bands at 1660, 1620,1565 and 1500 cm⁻¹.

EXAMPLE XXXVI Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-butyroylhydrazine##STR60## Method A

Into a 3-necked 250 ml flask was introduced butyric hydrazide (5.1 g,0.05 mole) and a 55% solution of methylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate in anhydrous methanol (22.0g, 0.05 mole). The flask was equipped with a magnetic stirrer, athermometer and a Dean Stark trap equipped with a reflux condenser. Theflask was placed in an oil bath and the reaction mixture was heated toreflux. The butyric hydrazide went into solution at about 30° C. Afterrefluxing 10-15 minutes, a solid material began to form. The methanolwas slowly distilled off by gradually draining the Dean Stark trap.After the methanol distillation stopped (75°-80° C.), the reactionmixture was a thick, viscous, taffy-like material. The reaction mixturewas diluted with 50 ml of methanol and refluxed until the reaction massdissolved (15 minutes). The solution was then cooled to 20° C. in a coldwater bath. Crystals began to form at about 40° C. The cold slurry wasfiltered and the filter cake was rinsed with a little cold, freshmethanol. The filter cake was air dried overnight. The dry productweighed 12.7 g (81.4% yield), had a melting range of 186°-190° C. andits infrared scan (nujol mull) contained carbonyl bands at 1660, 1620,1570 and 1500 cm⁻¹.

The methanol filtrate was concentrated on a rotating evaporator leaving4.5 g of a viscous liquid. Liquid chromatography indicated that thisviscous liquid was a mixture of the product and the two startingmaterials, suitable for recycling.

Method B

Into a 3-necked 250 ml flask was introduced HALS-O (12.2 g, 0.05 mole)and 150 ml THF. The flask was equipped with a magnetic stirrer, athermometer, a reflux condenser and a dropping funnel containing butyricanhydride (7.9 g, 0.05 mole) diluted to 15 ml with THF. The stirrer wasactivated and the butyric anhydride solution was added dropwise over 7minutes. The reaction temperature slowly rose from 18° C. to 22° C. Thereaction mixture was then heated to reflux in an oil bath for 1 hour.The reaction mixture was cooled to 60° C. and the insoluble material wasfiltered off and air dried. The dry product weighed 9.2 g and had amelting range of 185-192° C. The product was slurried in refluxingisopropanol for 10 minutes, refiltered and dried. The dry productweighed 6.5 g (40% yield), had a melting range of 185°-191° C. and itsinfrared scan was essentially the same as the product prepared in MethodA.

The THF and isopropanol filtrates were stripped to dryness on a rotatingevaporator. Infrared and liquid chromatography scans indicated theresidues were primarily the butyric acid salt of the desired productplus a small amount of the desired product.

EXAMPLE XXXVII Preparation of2,2'-Di-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]adipic dihydrazide##STR61##

Into a 3-necked 100 ml flask was introduced adipic dihydrazide (4.35 g,0.025 mole) and a 55% solution of methylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate in anhydrous methanol (22.0g, 0.05 mole). The flask was equipped with a magnetic stirrer, athermometer and a Dean Stark trap equipped with a reflux condenser. Theflask was placed in an oil bath and the reaction mixture was heated toreflux. The reaction mixture was refluxed 1/2 hour after which themethanol was slowly distilled off by gradually draining the Dean Starktrap. The reaction was refluxed for approximately 4 hours before thedistillation was stopped. The reaction mixture was diluted with 50 ml ofmethanol, refluxed 5 minutes and cooled to 60° C. The white solid thathad formed was filtered off, rinsed with fresh methanol and air dried.The dry product weighed 12.6 g (84.6% yield) and had a melting range of165°-175° C. The infrared scan of the product contained carbonyl bandsat 1670, 1625 (weak), 1585 and 1500 cm⁻¹.

EXAMPLES XXXVIII-XLVII Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-acylhydrazines##STR62##

EXAMPLES XXXVIII-XLVII were prepared using Method A of Example XXXVI.Into a 3-necked 250 ml flask was introduced 0.05 mole of the appropriatehydrazide and a 55% solution of methylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate in anhydrous methanol (22.0g, 0.05 mole). The flask was equipped with a magnetic stirrer, athermometer and a Dean Stark trap equipped with a reflux condenser. Theflask was placed in an oil bath and the reaction mixture was heated toreflux. The methanol was slowly distilled off by gradually draining theDean Stark trap. After the methanol distillation stopped, the reactionmixture was heated an additional 30-60 minutes at 90°-110° C. Thereaction mixture was then carefully diluted with 50-100 ml of methanoland was allowed to reflux 15-30 minutes. If the product did not dissolvein the hot methanol, it was isolated by filtration. If the product wassoluble in hot methanol, attempts were made to crystallize it out ofmethanol by cooling the methanol solution in a freezer (-5° C.). If theproduct would not crystallize out of methanol, the methanol was strippedoff under vacuum on a rotating evaporator. A vacuum pump and a heat gunwere employed to drive off the last traces of methanol, therebyconverting the residue from a sticky viscous liquid to a hardcrystalline solid. The solid was then scraped out of the evaporatingflask and pulverized with a mortar and pestle. The results aresummarized in Table III.

                                      TABLE III                                   __________________________________________________________________________    1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-acylhydrazines              ##STR63##                                                                                 Starting                                                                            Yield    m.p. Method of                                                                           IR Carbonyl Bands                      Example #                                                                           R.sup.15                                                                             Hydrazide                                                                           grams                                                                             % Yield                                                                            °C.                                                                         Isolation                                                                           cm.sup.-1                              __________________________________________________________________________    XXXVIII                                                                             (CH.sub.3).sub.2 CH                                                                  Isobutyric                                                                          13.8                                                                              88.5 216-220                                                                            filt. 1665, 1630, 1580,                                                             1510                                   XXXIV C.sub.4 H.sub.9                                                                      Valeric                                                                             12.4                                                                              76.1 162-167                                                                            crystn.                                                                             1665, 1630, 1580,                                                             1510                                   XL    C.sub.5 H.sub.11                                                                     Caproic                                                                             10.3                                                                              60.5 142-145                                                                            crystn.                                                                             1665, 1625, 1585,                                                             1500                                   XLI   C.sub.6 H.sub.13                                                                     Heptanoic                                                                           17.7                                                                              100   99-110                                                                            crystn.                                                                             1665, 1580, 1500                       XLII  C.sub.7 H.sub.15                                                                     Caprylic                                                                            15.0                                                                              81.5  98-102                                                                            crystn.                                                                             1665, 1580, 1495                       XLIII C.sub.9 H.sub. 19                                                                    Decanoic                                                                            19.8                                                                              100  83-87                                                                              evapn.                                                                              1660, 1585, 1500                       XLIV  C.sub.13 H.sub.27                                                                    Myristic                                                                            21.5                                                                              95.1 81-88                                                                              evapn.                                                                              1660, 1585, 1500                       XLV   C.sub.15 H.sub.31                                                                    Palmitic                                                                            20.5                                                                              85.4 77-87                                                                              evapn.                                                                              1665, 1585, 1500                       XLVI  C.sub.6 H.sub.5                                                                      Benzoic                                                                             12.5                                                                              72.2 221-223                                                                            filt. 1665, 1580, 1565                                                              1510                                   XLVII                                                                                ##STR64##                                                                           Salicylic                                                                           17.55                                                                             97.0 >300 filt. 1660, 1610, 1590 1550                  __________________________________________________________________________

EXAMPLE XLVIII Preparation of the Valetic Acid Salt of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-valeroylhydrazine##STR65##

Into a 3-necked 500 ml flask was introduced HALS-O (24.2 g, 0.1 mole)and 300 ml of THF. The flask was equipped with a magnetic stirrer, athermometer, a reflux condenser and a dropping funnel containing valeticanhydride (18.6 g, 0.1 mole). The stirrer was activated and theanhydride was added over 15 minutes. The temperature gradually rose from18° C. to 25° C. The reaction mixture was heated to reflux in an oilbath for 1 hour. The hot reaction mixture (60° C.) was filtered toremove some insoluble material.

The filter cake weighed 1.6 g after drying and its infrared scan was thesame as the product prepared in Example XXXIX indicating it was theuncomplexed1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-valeroylhydrazine.

The THF filtrate was concentrated to dryness on a rotating evaporatorunder reduced pressure. The residue was slurried in 100 ml ofisopropanol, filtered and the filter cake was dried. The dry productweighed 36.6 g and had a melting range of 155°-170° C. A second crop of2.4 g was obtained by stripping off the isopropanol, slurrying theresidue in hexane and filtering off the solid product. The infraredscans of the two crops showed a very strong carbonyl band at 1645 cm⁻¹with a weak shoulder at 1660 cm⁻¹, a broad carbonyl at 1550 cm⁻¹ andsharp weaker bands at 1520 and 1490 cm⁻¹. The combined yield was 39.0 gor a 91.3% yield for the acid salt. A TGA scan of the product indicatedit lost 27% (theoretrical is 24%) of its weight upon heating from 150°C. to 260° C. The TGA scan indicated that the salt dissociated uponheating and slowly evolved valetic acid.

EXAMPLE XLIX Preparation of the Hexanoic Acid Salt of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-hexanoylhydrazine##STR66##

The hexanoic acid salt was prepared in the same manner as the valericacid salt of Example XLVIII with the exception that 0.1 mole of hexanoicanhydride was substituted for the valeric anhydride. No insolublematerial formed in the hot THF reaction mixture. The product wasisolated by stripping off the THF, slurrying the residue in isopropanol,filtering off the insoluble material and drying the filter cake. Theyield was 42.7 g (93.5% yield). The product had a melting range of155°-162° C. and its infrared scan (nujol mull) contained a very strong,sharp carbonyl band at 1650 cm⁻¹ and weaker carbonyl bands at 1620, 1540and 1490 cm⁻¹. A TGA scan of the product indicated it lost 28%(theoretical is 25.5%) of its weight upon heating from 150° to 260° C.The TGA scan indicated that the salt dissociated upon heating and slowlyevolved hexanoic acid.

EXAMPLE L Preparation of the Heptanoic Acid Salt of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-heptanoylhydrazine##STR67##

The heptanoic acid salt was prepared in the same manner as the valeticacid salt of Example XLVIII with the exception that 0.1 mole ofheptanoic anhydride was substituted for the valetic anhydride and thereaction mixture was not heated. After stirring for two hours at roomtemperature, the reaction mixture solidified. The reaction mixture wasallowed to stand overnight and the solid product was filtered off thenext morning. After drying, the product weighed 32.2 g and had a meltingrange of 140°-150° C.

An additional 7.3 g of product was isolated by concentrating the THFfiltrate, slurrying the residue in isopropanol, filtering off and dryingthe insoluble material. The total yield was 39.5 g (81.5% yield).

The infrared scan of the product contained a very strong, sharp carbonylband at 1660 cm⁻¹ with weaker carbonyl bands at 1615, 1545 and 1490cm⁻¹. A TGA scan of the product indicated it lost 30% (theoretical is27%) of its weight upon heating from 150° C. to 260° C. The TGA scanindicated that the salt dissociated upon heating and slowly evolvedheptanoic acid.

EXAMPLES LI-XCVII Preparation, Weathering and Evaluation of Tensile BarsContaining Derivatives of HALS Substituted Amic Acid Hydrazides

Dry blends of Himont™ 6501 polypropylene, various HALS amic acidhydrazide derivatives and optionally a small amount of a hindered phenolantioxidant (Irganox™ 1076) were prepared in a polyethylene container(for composition, see Table IV). The blends were shaken well to insure agood dispersion of the additives in the polypropylene. The blends werethen extruded on a Brabender Prep Center Extruder Model No. 1340 havinga 11/4 inch screw diameter with a length to diameter ratio of 25:1. Theextruder was operated at a screw speed of 30 RPM and all of the heatingzones were controlled at 200° C. The first 100 g of extrudate were usedto purge out the extruder between runs and was discarded. The remainingextrudate was air cooled and pelletized. The concentration of the2,2,6,6-tetramethyl-4-piperidinyl group in the polypropylene wasapproximately 0.3%. The concentration of the Irganox™ 1076 (when used)was approximately 0.25%. UV-Chek™ AM-340 was included in some blends asa synergist at a concentration of 0.22%.

The pellets were injection molded in a Newbury 25 ton injection moldingmachine at 400° F. into 73/8"×3/4"×1/8" tensile bars.

A control sample containing only Irganox™ 1076 was included forcomparison. Control samples containing Irganox™ 1076 and Ciba-Geigy'sChimasorb™ 944 and Tinuvin™ 770 were also included for comparison.

The tensile bars were placed in a QUV Accelerated Weather Tester (QPanel Company) for various exposure times. The QUV operated with an 8hour light cycle using UV-B bulbs at 60° C. and a 4 hour condensationcycle at 50° C. Samples were placed in the QUV and withdrawnperiodically at the same time of day. The tensile bars were pulled on aninstrumented Instron (Model 4204) according to ASTM Procedure 638. Theminimum QUV exposure time interval required to obtain a brittle break inthe Instron test was determined. A result was considered a brittle breakwhen the tensile bar snapped before 15% elongation was obtained.

The QUV time interval required to generate spotting and clouding of thesurface of the tensile bars was also noted. The results are summarizedin Table IV.

Tensile bars were also exposed to UV-A bulbs in a QUV under the sameconditions for 60 days. A few were also tested after longer intervals.The tensile bars were then pulled on the Instron. A brittle break wasconsidered a failure and greater than 15% elongation was consideredpassing. These results are also summarized in Table IV.

                                      TABLE IV                                    __________________________________________________________________________    STABILIZATION OF POLYPROPYLENE WITH HALS AMIC ACID DERIVATIVES                      HALS                                                                          COM-       POLY-             DAYS TO                                                                             DAYS TO                              EX-   POUND      PROPY-                                                                              IRGANOX                                                                             UV CHEK                                                                             SPOT- BRITTLE                                                                             PASS-FAIL IN QUV-A             AMPLE EXAM-      LENE  1076  AM-340                                                                              TING  BREAK 60  80  100 120                #     PLE # GRAMS                                                                              (GRAMS)                                                                             (GRAMS)                                                                             (GRAMS)                                                                             IN QUV-B                                                                            IN QUV-B                                                                            DAYS                                                                              DAYS                                                                              DAYS                                                                              DAYS               __________________________________________________________________________    LI    II    3.45 445   --    --    19-21 >30<35                                                                              NT                             LII   II    3.45 445   1.1   --    26-28 >30<35                                                                              NT                             LIII  III   3.25 445   --    --    >50<70                                                                              >50<70                                                                              PASS                           LIV   III   3.25 445   1.1   --    >50<70                                                                              >50<70                                                                              PASS                                                                              PASS                       LV    III   3.25 445   --    1.0   >70   >70   PASS                                                                              PASS                                                                              PASS                                                                              PASS               LVI   IV    5.1  445   --    --    >50<60                                                                              >50<60                                                                              PASS                           LVII  IV    5.1  445   1.1   --    >50<60                                                                              >50<60                                                                              NT                             LVIII V     3.5  445   --    --    >45<50                                                                              >35<40                                                                              PASS                           LIX   V     3.5  445   1.1   --    >50   >35<40                                                                              NT                             LX    VI    3.8  445   --    --    >35<40                                                                              >20<30                                                                              NT                             LXI   VI    3.8  445   1.1   --    >35<40                                                                              >30<35                                                                              NT                             LXII  IX    3.0  445   --    --    <12   >25<30                                                                              NT                             LXIII IX    3.0  445   1.1   --    19    >25<30                                                                              NT                             LXIV  X     3.4  445   --    --    >40<50                                                                              >40<50                                                                              PASS                           LXV   X     3.4  445   1.1   --    >40<50                                                                              >50<70                                                                              NT                             LXVI  XI    3.5  445   --    --    >30<40                                                                              >30<35                                                                              FAIL                           LXVII XI    3.5  445   1.1   --    >35<40                                                                              >40<50                                                                              PASS                           LXVIII                                                                              XII   4.2  445   --    --    >50   >50<70                                                                              PASS                                                                              PASS                       LXIX  XII   4.2  445   1.1   --    >50   >50<70                                                                              PASS                           LXX   XV    2.7  445   --    --    35    >40<50                                                                              PASS                           LXXI  XV    2.7  445   1.1   --    >50   >50<70                                                                              NT                             LXXII XVI   2.8  445   --    --    >50<70                                                                              >50<70                                                                              PASS                                                                              PASS                       LXXIII                                                                              XVI   2.8  445   1.1   --    >50<70                                                                              >50<70                                                                              NT                             LXXIV XVI   2.8  445   --    1.0   >70   >70   PASS                                                                              PASS                                                                              PASS                                                                              PASS               LXXV  XVII  3.1  445   --    --    >50   >40<50                                                                              NT                             LXXVI XVII  3.1  445   1.1   --    >50   >40<50                                                                              NT                             LXXVII                                                                              XVIII 1.0  250   --    --    >30   >30   NT                             LXXVIII                                                                             XXI   4.6  445   --    --    >60<70                                                                              >70   PASS                                                                              PASS                                                                              PASS                                                                              PASS               LXXIX XXI   4.6  445   --    1.0   >70   >70   PASS                                                                              PASS                                                                              PASS                                                                              PASS               LXXX  XXII  3.0  445   --          >40<50                                                                              >40<50                                                                              PASS                                                                              PASS                                                                              PASS                                                                              PASS               LXXXI XXII  3.0  445   1.1   --    >40<50                                                                              >50<60                                                                              PASS                                                                              PASS                                                                              PASS                                                                              PASS               LXXXII                                                                              XXV   4.5  445   --    --    >35<40                                                                              >35<40                                                                              NT                             LXXXIII                                                                             XXV   4.5  445   1.1   --    40    >35<40                                                                              NT                             LXXXIV                                                                              XXVI  4.9  445   --    --    >60<70                                                                              >70   PASS                                                                              PASS                                                                              PASS                   LXXXV XXVI  4.9  445   1.1   --    >60<70                                                                              >60<70                                                                              PASS                                                                              PASS                                                                              PASS                   LXXXVI                                                                              XXX   4.9  445   --    --    <20   >20<25                                                                              NT                             LXXXVII                                                                             XXXIII                                                                              2.4  445   --    --    >30<35                                                                              >35<40                                                                              PASS                           LXXXVIII                                                                            XXXIII                                                                              2.4  445   1.1   --    40    >40<50                                                                              NT                             LXXXIX                                                                              VII   3.6  445   --    --    >35<40                                                                              >35<40                                                                              FAIL                           XC    VIII  5.5  445   --    --    >35<40                                                                              >30 35                                                                              PASS                           XCI   VIII  5.5  445   1.1   --    >40   >30<35                                                                              PASS                           XCII  XIII  3.7  445   --    --    <30    15 15                                                                              PASS                           XCIII XIII  3.7  445   1.1   --    >30<35                                                                              >30<35                                                                              PASS                           XCIV  XIV   3.5  445   --    --    >25<30                                                                              >25<30                                                                              PASS                           XCV   XIV   3.5  445   1.1   --    >30<35                                                                              >30<35                                                                              PASS                           XCVI  XX    3.2  445   --    --    >30<40                                                                               12 15                                                                              FAIL                           XCVII XX    3.2  445   1.1   --    >40   >15<20                                                                              PASS                           C-1   --    --   445   1.1   --    >5<7  > 4<5 FAIL                           C-2   TINUVIN                                                                             2.3  445   1.1   --    >35   >20<25                                                                              FAIL                                 770                                                                     C-3   CHIMA-                                                                              2.85 445   1.1   --    >33<35                                                                              >20<25                                                                              FAIL                                 SORB 944                                                                __________________________________________________________________________     NT = NOT TESTED                                                          

The results obtained indicate that the compounds evaluated are very goodlight stabilizers and are more efficient than Tinuvin™ 770 and Chimasorb944 upon exposure to both UV-A and UV-B light.

EXAMPLE XCVIII Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl)hydrazine##STR68## Method A--Preparation of Phenyl1,2,2,6,6-Pentamethyl-4-piperidinyl Carbonate

Into a 500 ml 3-neck flask was added 17.1 grams (0.1 mole)1,2,2,6,6-pentamethyl-4-piperidinol and 300 mls of methyl t-butyl ether(MtBE). The flask was equipped with a magnetic stirrer, thermometer,reflux condenser and dropping funnel containing 15.6 grams (0.1 mole)phenyl chloroformate. The phenyl chloroformate was slowly added to the1,2,2,6,6-pentamethyl-4-piperidinol solution without any appreciableexotherm. Then 11.2 grams (0.1 mole) of 1,4-diazabicyclo(2.2.2)octane(DABCO) was added at room temperature. The temperature rose to 50° C.and a precipitate formed. The reaction was stirred for 2 hours, anadditional 2 grams of DABCO and 1.25 grams of phenyl chloroformate wasadded, the reaction heated to reflux and refluxed 2 hours. The reactionmixture was cooled, transferred to a separatory funnel and washed withwater to remove DABCO, DABCO hydrochloride and a small amount of1,2,2,6,6-pentamethyl-4-piperidinol. The product was then extracted outof the MtBE layer with 100 mls of 5% HCl diluted with water to 400 mls.The MtBE layer which contained diphenyl carbonate was discarded. Theacid layer was made basic with 100 ml of 10% NaOH. The product wasextracted out of the aqueous layer with 200 ml MtBE. The MtBE extractwas washed with 100 ml 5% NaHCO₃, dried over anhydrous MgSO₄, filteredand the MtBE stripped off on a rotating evaporator under reducedpressure. The residue was a white solid weighing 20.4 grams (70.1% crudeyield) which had a melting point of 63°-67° C. Liquid chromatographyindicated the product was essentially one component. The infraredspectrum contained a strong carbonyl peak at 1755 cm⁻¹.

Method B--Preparation of 1,2,2,6,6-Pentamethyl-4-piperidinyl Carbazate

Into a 250 ml 3-neck flask was added 20.0 grams (0.069 mole) of phenyl1,2,2,6,6-pentamethyl-4-piperidinyl carbonate and 100 mls of methanol.The flask was equipped with a magnetic stirrer, thermometer, refluxcondenser and dropping funnel containing 3.8 grams (0.076 mole) of 64%aqueous hydrazine. The hydrazine was added slowly to the stirringmethanol solution at room temperature. There was a slight exotherm. Thereaction mixture was stirred for 5 hours at room temperature at whichpoint liquid chromatography indicated the reaction was complete. Themethanol was stripped off on a rotating evaporator under reducedpressure and the residue was dissolved in 150 ml MtBE. The MtBE solutionwas washed 3 times with 25 ml portions of 5% NaOH saturated with sodiumchloride to remove the phenol that was generated. The MtBE layer wasdried over anhydrous MgSO₄, filtered and the MtBE stripped off on arotating evaporator under reduced pressure. The residue was a whitesolid (m.p. 90°-94° C.) weighing 14.3 grams (90.5% crude yield). Liquidchromatography indicated the product was one component. The infraredspectrum contained a strong carbonyl peak at 1710 cm⁻¹ and a moderatepeak at 1625 cm⁻¹.

Method C--Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl)hydrazine

Into a 100 ml 3-neck flask was added 7.3 grams (0.0318 mole) of1,2,2,6,6-pentamethyl-4-piperidinyl carbazate, 12.9 grams (0.032 mole)of a 60% solution of ethyl N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamatein methanol and 15 ml of methanol. The flask was equipped with amagnetic stirrer, thermometer and a Dean Stark trap with refluxcondenser. The flask was placed in a hot oil bath and heated to reflux.The methanol was distilled off through the Dean Stark trap and theresidue was heated for 4 hours at 75°-80° C. Liquid chromatography ofthe residue indicated that the reaction had proceeded to 85-90% ofcompletion. The reaction was cooled to 50° C. and 50 ml of methanol wasadded to dissolve the product. The methanol solution was cooled in thefreezer (-10° C.) overnight and the next day the crystals that formedwere filtered off and air dried. The dry crystals weighed 3.1 grams andmelted at 165°-170° C. A liquid chromatography scan indicated thepresence of only one component. The infrared spectrum of the productcontained a weak carbonyl peak at 1740 cm⁻¹ and strong, sharp carbonylpeaks at 1600 and 1685 cm⁻¹. A second crop of 4.5 grams was obtained byconcentrating the filtrate to about 25 ml, cooling and filtering off thesolids that formed. The filtrate was stripped to dryness, leaving 7.0grams of product which was contaminated with small amounts of thestarting materials.

EXAMPLE XCIX1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-(2,2,6,6-tetramethyl-4-piperidinyloxycarbonyl)hydrazine##STR69## Method A--Preparation of Phenyl2,2,6,6-Tetramethyl-4-piperidinyl Carbonate

Into a 500 ml 3-neck flask was added 23.2 grams (0.14 mole) of 95%2,2,6,6-tetramethyl-4-piperidinol and 400 ml of methylene chloride. Theflask was equipped with a magnetic stirrer, thermometer, refluxcondenser and dropping funnel containing 11.2 grams (0.07 mole) ofphenyl chloroformate. The phenyl chloroformate was slowly added to the2,2,6,6-tetramethyl-4-piperidinol solution without any appreciableexotherm. Then 0.5 grams of 1,4-diazabicyclo(2.2.2)octane (DABCO) wasadded at room temperature. The temperature rose to 35° C. and aprecipitate formed. Another 0.5 gram of DABCO was added but no furtherexotherm occurred. After stirring for 11/2 hours, the solids werefiltered off and the methylene chloride solution was washed with water,10% NaOH and water again, dried over anhydrous MgSO₄, filtered and thesolvent stripped off on a rotating evaporator under reduced pressure.The residue was a white solid weighing 17.4 grams (90% crude yield)which had a melting point of 62°-65° C. Liquid chromatography indicatedthe product was essentially one component. The infrared spectrumcontained a strong carbonyl peak at 1760 cm⁻¹ and a moderate carbonylpeak at 1710 cm.sup. -1.

Method B--Preparation of 2,2,6,6-tetramethyl-4-piperidinyl Carbazate

Into a 300 ml 3-neck flask were added 16.9 grams (0.061 mole) of phenyl2,2,6,6-tetramethyl-4-piperidinyl carbonate and 100 ml of methanol. Theflask was equipped with a magnetic stirrer, thermometer, refluxcondenser and dropping funnel containing 3.4 grams (0.067 mole) of 64%aqueous hydrazine. The hydrazine was added slowly to the stirringmethanol solution at room temperature. There was a slight exotherm. Thereaction mixture was stirred for 3 hours and then allowed to standovernight (i.e. for 20 hours) at room temperature. The next day, themethanol was stripped off on a rotating evaporator and the liquidresidue dissolved in 150 ml of MtBE and washed with 50 ml of 10% NaOHwhich was saturated with salt. The MtBE solution was dried overanhydrous MgSO₄, filtered and the MtBE stripped off on a rotatingevaporator under reduced pressure. The residue, a very viscous liquid,was slurried in 20 ml of hexane until a solid formed. The solid wasfiltered off and air dried. The product weighed 6.4 grams (49% crudeyield), had a melting point of 93°-94° C. and gas chromatographyindicated it was about 95% pure. The infrared scan contained a strongcarbonyl peak at 1710 cm⁻¹ and a moderate carbonyl peak at 1625 cm⁻¹. Anadditional 5.26 grams of crude product was recovered by extracting theaqueous wash with methylene chloride and stripping off the solvent.

Method C--Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-(2,2,6,6-tetramethyl-4-piperidinyloxycarbonyl)hydrazine

Into a 100 ml 3-neck flask was added 7.3 grams (0.0318 mole) of1,2,2,6,6-pentamethyl-4-piperidinyl carbazate, 12.9 grams (0.032 mole)of a 60% solution of ethyl N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamatein methanol and 15 ml of methanol. The flask was equipped with amagnetic stirrer, thermometer and a Dean Stark trap with refluxcondenser. The flask was placed in a hot oil bath and heated to reflux.The methanol was distilled off through the Dean Stark trap and theresidue was cooked for 4 hours at 75°-80° C. Liquid chromatography ofthe residue indicated the reaction had gone to 85-90% of completion. Thereaction was cooled to 50° C. and 50 ml of methanol was added todissolve the product. The methanol solution was cooled in the freezer(at -10° C.) overnight and the next day, the crystals that formed werefiltered off and air dried. The dry crystals weighed 3.1 grams andmelted at 165°-170° C. A liquid chromatography scan indicated thepresence of only one peak. The infrared spectrum of the productcontained a weak carbonyl peak at 1740 cm⁻¹ and strong, sharp carbonylpeaks at 1600 and 1685 cm⁻¹. A second crop of 4 5 grams was obtained byconcentrating the filtrate to about 25 ml, cooling and filtering off thesolids that formed. The filtrate was stripped to dryness, leaving 7.0grams of product which was contaminated with small amounts of thestarting materials.

EXAMPLE C Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[2-(3-hydroxy-4-benzoylphenoxy)ethoxycarbonyl]hydrazine##STR70## Method A--Preparation of 2-(3-Hydroxy-4-benzoylphenoxy)ethylCarbazate

Into a 250 ml 3-neck flask was added 5.4 grams (0.11 mole) of 64%aqueous hydrazine and 50 mls of THF. The flask was equipped with amagnetic stirrer, thermometer, reflux condenser and a dropping funnelcontaining 9.6 grams (0.03 mole) of 2-(3-hydroxy-4-benzoylphenoxy)ethylchloroformate dissolved in 50 ml of THF. The chloroformate solution wasadded dropwise to the stirring hydrazine solution over 1/2 hour. Thetemperature quickly exothermed to 36° C. and slowly subsided after theaddition was over. The reaction was stirred an additional 1/2 hour andconcentrated to 31 grams. The THF solution was added to 300 ml of water.A sticky solid formed. The solid was filtered off, taken up in methylenechloride, dried over Na₂ SO₄, filtered and the methylene chloridestripped off. The residue was a viscous orange-brown liquid. The crudeproduct was slurried in 150 ml of warm MtBE. Most of the crude productwent into solution, leaving a dark brown liquid residue. The yellow MtBElayer was decanted off and the MtBE stripped off on a rotatingevaporator, leaving 9.0 grams of a yellow viscous liquid. Liquidchromatography indicated it was about 92% pure. The residue was slurriedin warm methanol and upon cooling, a solid formed. The solid wasfiltered off and after air drying, weighed 6.4 grams (67% yield) and hada melting point of 58°-61° C.

Method B--Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-[2-(3-hydroxy-4-benzoylphenoxy)ethoxycarbonyl]hydrazine

Into a 100 ml 3-neck flask was added 6.4 grams (0.027 mole) of2-(3-hydroxy-4-benzoylphenoxy)ethyl carbazate from (A), 8.1 grams (0.027mole) of a 60% solution of ethylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate and 25 ml of methanol. Theflask was equipped with a magnetic stirrer, thermometer and a Dean Starktrap with a reflux condenser. The reaction was heated in an oil bath andthe methanol was slowly distilled off through the Dean Stark trap. Afterthe methanol stopped coming over, the reaction was heated one hour, avacuum was applied to the system to remove any residual methanol and thereaction was heated for another 11/2 hours at 70° C. The reaction wasdissolved in 50 ml of hot methanol. The solution was filtered to removea small amount of insoluble material. The methanol was stripped from thefiltrate on a rotating evaporator, leaving 9.4 grams of a yellowcrystalline solid. Liquid chromatography indicated the product was about85-90% pure.

EXAMPLE CI Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)-oxamoyl]-2-(allyloxycarbonyl)hydrazine##STR71## Method A--Preparation of Allyl Carbazate

Allyl phenyl carbonate was prepared in 97% yield by reacting 17.6 grams(0.3 mole) of allyl alcohol with 48.4 grams (0.3 mole) of phenylchloroformate in the presence of 26.4 grams (0.33 mole) of pyridine and300 ml of methylene chloride. The allyl phenyl carbonate soluation waswashed with 5% HCl, water, dried over anhydrous sodium sulfate, filteredand the methylene chloride evaporated on a rotating evaporator underreduced pressure. The residual allyl phenyl carbonate (52.7 grams--0.29mole) was dissolved in 200 ml of methanol and treated with 16.0 grams(0.32 mole) of 64% aqueous hydrazine at room temperature. After twohours, gase chromatography indicated that the carbonate had beencompletely converted to allyl carbazate and phenol. The reaction mixturewas stripped of volatiles on the rotating evaporator. The residue wastaken up in 200 ml of methylene chloride and washed with 50 grams of 25%sodium hydroxide to remove the phenol. The methylene chloride layer waswashed with saturated salt solution, dried over sodium sulfate, filteredand the methylene chloride stripped off on the rotating evaporator. Theresidue weighed 9.2 grams and assayed 98.0% by gas chromatography. Anadditional 3.9 grams was recovered by reextracting the aqueous wash.

Method B--Preparation of1-[N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamoyl]-2-(allyloxycarbonyl)hydrazine

Into a 250 ml 3-neck flask was added 9.2 grams (0.079 mole) of allylcarbazate from (A), 34.2 grams (0.08 mole) of a 60% solution of ethylN-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate and 50 ml of methanol. Theflask was equipped with a magnetic stirrer, thermometer and a Dean Starktrap with a reflux The reaction was heated in an oil bath and themethanol was distilled off through the Dean Stark trap. After themethanol distillation ceased, a vacuum was applied to the system toremove any residual methanol and the reaction was cooked for 80 minutesat 90° C. The reaction was cooled to 50° C. and 50 ml of methanol wasadded and the reaction heated back up to reflux to dissolve the residue.The methanol solution was cooled and concentrated to 25 ml. Uponaddition of 25 ml of methyl t-butyl ether, a white solid formed. Thesolid was filtered off and dried in a vacuum oven over night. The drypowder weighed 22.1 grams (85.7% yield) and assayed 100% by liquidchromatography. The infrared scan of the product contained a weakcarbonyl at 1750 cm⁻¹ and a strong carbonyl at 1680 cm⁻¹.

COMPARATIVE EXAMPLE

It is well known that many hindered amine light stabilizers, especiallyin the presence of hindered phenol antioxidants, discolor polyolefinsthey are stabilizing upon exposure to high temperatures. The followingexample compares the discoloration of polypropylene tensile barscontaining the compounds of U.S. Pat. No. 4,824,884 (assigned to thepresent assignee) and tensile bars containing equivalent amounts of thecompounds of the present invention upon heat aging at varioustemperatures and time periods. The compounds were compared on the basisof their ability at low concentrations to stabilize polypropylene withreduced discoloration when polypropylene tensile bars containing theindicated stabilizers were exposed to high temperatures.

All of the tensile bars were prepared in accordance with the methoddescribed above for Examples LI-XCVII. The tensile bars were heat agedin a Blue M™ forced air oven at the indicated temperatures and timeintervals. The Yellowness Index values were determined on a ColorgardSystem/05™ colorimeter manufactured by Pacific Scientific. The tensilebars were prepared and tested both with and without the presence of asecondary antioxidant as indicated in the following tables.

Tables A and B qualitatively demonstrate the discoloration of tensilebars containing the compounds of U.S. Pat. No. 4,824,884 upon heat agingat 140° C. in both the presence and absence of antioxidants.

In order to contrast the compounds of the present invention from thoseof U.S. Pat. No. 4,824,884, Table C qualitatively demonstrates thecomparatively slow buildup of color in tensile bars containing compoundsfalling within the scope of the present invention upon heat aging at135° C. for up to 25 days. Similarly, Table D demonstrates the slowincrease in color buildup in the tensile bars containing the compoundsof the present invention over 50 and 100 day periods at 135° C. Theresults set forth in Tables C and D indicate that no significantdifference in color buildup results whether the sample contains anantioxidant or not.

Tables E and F quantitatively illustrate the difference between thepresent compounds and those of U.S. Pat. No. 4,824,884 with respect tothe change in Yellowness Index (ΔYID) upon heat aging at 120° C. for 1and 3 days and 140° C. for 3 and 6 days both with and without theconcomittant use of secondary antioxidants.

                                      TABLE A                                     __________________________________________________________________________    Heat Aging Results at 140° C.                                          Compounds of U.S. Pat. No. 4,824,884                                          Tensile                                                                            Patent         Initial                                                   Bar No.                                                                            Example No.                                                                          Antioxidant                                                                           Color                                                                              1 Day 5 Days                                                                              20 Days                                  __________________________________________________________________________    126  XII    --      colorless                                                                          yellow                                                                              brown dk. brown                                127  XII    1076.sup.1                                                                            colorless                                                                          yllow-brn                                                                           dk. brown                                                                           dk. brown                                128  XII    168.sup.2                                                                             colorless                                                                          lt. straw                                                                           orng-yllow                                                                          dk. brown                                130  XI     --      colorless                                                                          yellow                                                                              brown dk. brown                                131  XI     168     colorless                                                                          strw-yllw                                                                           brown dk. brown                                132  XI     1076/DBHA.sup.3                                                                       colorless                                                                          brown brown dk. brown                                133  XII    Naugard XL-1.sup.4                                                                    colorless                                                                          brown dk. brown                                                                           dk. brown                                134  XII    1076/DBHA                                                                             colorless                                                                          brown dk. brown                                                                           dk. brown                                138  VIIA   --      colorless                                                                          lt. brown                                                                           dk. brown                                                                           dk. brown                                139  VIIA   1076    colorless                                                                          dk. brown                                                                           dk. brown                                                                           dk. brown                                __________________________________________________________________________     .sup.1 Irganox ™ 1076 [octadecyl 3(3,5-di-.sub.-                           tbutyl-4-hydroxyphenyl)propionate] is a phenolic antioxidant and was          obtained from CibaGeigy Corp.                                                 .sup.2 Irgafos ™ 168 [tris(2,4di-.sub.- tbutylphenyl)phosphite] is a       nonphenolic antioxidant and was obtained from CibaGeigy Corp.                 .sup.3 N,NDibenzylhydroxylamine (DBHA) was purchased from Aldrich Chemica     Co.                                                                           .sup.4 Naugard ™ XL1,2,2oxamido bis[ethyl 3(3,5-di-.sub.-                  tbutyl-4-hydroxyphenyl)propionate] is a phenolic antioxidant and was          obtained from Uniroyal Chemical Co.                                      

                  TABLE B                                                         ______________________________________                                        140° C. Heat Aging Tests                                               Compounds of U.S. Pat. No. 4,824,884                                          Effect of Antioxidant on Color Upon Heat Aging                                Tensile                                                                             Patent                                                                  Bar   Example                    Color After 5                                No.   No. of HALS                                                                              Antioxidant     Days at 140° C.                       ______________________________________                                        186   XI         none            dark brown                                    80   XI         Irganox 1076    dark brown                                   131   XI         Irgafos 168     dark brown                                   132   XI         Irganox 1076 + DBHA                                                                           brown                                        188   XI         0.1% UV-Chek AM-340.sup.5                                                                     dark brown                                   187   XI         0.2% UV-Chek AM 340                                                                           dark brown                                   189   XI         0.2% Cyasorb 2908.sup.6                                                                       dark brown                                   182   XII        none            dark brown                                   127   XII        Irganox 1076    dark brown                                   128   XII        Irgafos 168     brown                                        133   XII        Naugard XL-1    brown                                        134   XII        Irganox 1076 + DBHA                                                                           brown                                        184   XII        0.1% UV-Chek AM-340                                                                           dark brown                                   183   XII        0.2% UV-Chek AM-340                                                                           dark brown                                   185   XII        0.2% Cyasorb 3908                                                                             dark brown                                   138   VII-A      none            dark brown                                   139   VII-A      Irganox 1076    dark rown                                    140   VII-A      Irganox 1076 +  dark brown                                                    Tridecyl phosphite                                           ______________________________________                                         .sup.5 UVChek ™ AM340 (2,4di-.sub.- tbutylphenyl 3,5di-.sub.-              tbutyl-4-hydroxybenzoate) was obtained from Ferro Corp.                       .sup.6 Cyasorb ™ 2908 (-nhexadecyl 3,5di-.sub.-                            tbutyl-4-hydroxybenzoate) is a phenolic antioxidant and was obtained from     the Polymer Additives Department of American Cyanamid Company.           

                                      TABLE C                                     __________________________________________________________________________    Heat Aging Results at 135° C.                                          Compounds of Present Invention                                                Tensile                                                                            Application    Initial                                                   Bar No.                                                                            Example No.                                                                          Antioxidant                                                                           Color                                                                              5 Days                                                                              10 Days                                                                             25 Days                                  __________________________________________________________________________    424  XLIII  --      colorless                                                                          lt. straw                                                                           dk. straw                                                                           lt. brown                                425  XLIII  1076    colorless                                                                          yllow-brn                                                                           yllow-brn                                                                           lt. brown                                426  XLIII   168    colorless                                                                          lt. straw                                                                           staw  lt. tan                                  432  XLIV   --      colorless                                                                          lt. straw                                                                           lt. brown                                                                           lt. brown                                433  XLIV   1076    v.lt.straw                                                                         yllow-brn                                                                           lt. brown                                                                           lt. brown                                434  XLIV    168    colorless                                                                          lt. straw                                                                           straw tan                                      452  XLV    --      colorless                                                                          lt. straw                                                                           dk. straw                                                                           lt. brown                                453  XLV    1076    v.lt.straw                                                                         yllow-brn                                                                           dk. brown                                                                           lt. brown                                454  XLV     168    colorless                                                                          lt. straw                                                                           straw lt. brown                                422  XXVI   --      colorless                                                                          lt. straw                                                                           lt. brown                                                                           lt. brown                                423  XXVI    168    colorless                                                                          lt. straw                                                                           straw lt. brown                                427  XXXVII --      colorless                                                                          colorless                                                                           lt. straw                                                                           off-white                                428  XXXVII  168    colorless                                                                          colorless                                                                           v.lt.straw                                                                          off-white                                420  XXXV   --      colorless                                                                          colorless                                                                           colorless                                                                           lt. straw                                421  XXXV   1076    colorless                                                                          colorless                                                                           lt. straw                                                                           lt. straw                                443  XXXVI  --      colorless                                                                          colorless                                                                           colorless                                                                           colorless                                444  XXXVI  1076    colorless                                                                          colorless                                                                           v.lt.straw                                                                          lt. straw                                445  XXXVI   168    colorless                                                                          colorless                                                                           colorless                                                                           colorless                                447  XXXVII --      colorless                                                                          colorless                                                                           colorless                                                                           colorless                                440  XXXIX  --      colorless                                                                          lt. straw                                                                           lt. straw                                                                           off-white                                441  XXXIX  1076    colorless                                                                          yllow-brn                                                                           yllow-brn                                                                           yllow-brn                                442  XXXIX   168    colorless                                                                          colorless                                                                           v.lt.straw                                                                          off-white                                438  XL     --      colorless                                                                          lt. straw                                                                           straw off-white                                439  XL     1076    colorless                                                                          yllow-brn                                                                           yllow-brn                                                                           yllow-brn                                435  XLI    --      colorless                                                                          lt. straw                                                                           straw off-white                                436  XLI    1076    colorless                                                                          yllow-brn                                                                           yllow-brn                                                                           yllow-brn                                437  XLI     168    colorless                                                                          v.lt.straw                                                                          lt. straw                                                                           off-white                                429  XLII   --      colorless                                                                          lt. straw                                                                           dk. straw                                                                           dk. straw                                430  XLII   1076    colorless                                                                          yllow-brn                                                                           yllow-brn                                                                           lt. brown                                431  XLII    168    colorless                                                                          lt. straw                                                                           straw off-white                                __________________________________________________________________________

                                      TABLE D                                     __________________________________________________________________________    Heat Aging Results at 135° C.                                          Compounds of Present Invention                                                Tensile                                                                            Application    Initial                                                   Bar No.                                                                            Example No.                                                                          Antioxidant                                                                           Color 50 days                                                                             100 Days                                      __________________________________________________________________________    420  XXXV   --      colorless                                                                           lt. straw                                                                           lt. straw                                     421  XXXV   1076    colorless                                                                           lt. straw                                                                           lt. straw                                     443  XXXVI  --      colorless                                                                           colorless                                                                           colorless                                     444  XXXVI  1076    colorless                                                                           lt. straw                                                                           lt. straw                                     445  XXXVI   168    colorless                                                                           colorless                                                                           colorless                                     447  XXXVII --      colorless                                                                           off-white                                                                           colorless                                     440  XXXIX  --      colorless                                                                           lt. straw                                                                            --                                           441  XXXIX  1076    colorless                                                                           lt. straw                                                                           lt. straw                                     442  XXXIX   168    colorless                                                                           colorless                                                                            --                                           438  XL     --      colorless                                                                           colorless                                                                            --                                           439  XL     1076    colorless                                                                           yellow                                                                              straw                                         435  XLI    --      colorless                                                                           lt. straw                                                                            --                                           436  XLI    1076    colorless                                                                           yellow                                                                              straw                                         437  XLI     168    colorless                                                                           lt. straw                                                                            --                                           429  XLII   --      colorless                                                                           dk. straw                                                                           straw                                         430  XLII   1076    colorless                                                                           lt. brown                                                                           lt. brown                                     431  XLII    168    colorless                                                                           colorless                                                                            --                                           424  XLIII  --      colorless                                                                           lt. brown                                                                           lt. brown                                     425  XLIII  1076    colorless                                                                           lt. brown                                                                           lt. brown                                     426  XLIII   168    colorless                                                                           lt. straw                                                                           lt. straw                                     432  XLIV   --      colorless                                                                           lt. brown                                                                           dk. brown                                     433  XLIV   1076    v.lt.straw                                                                          lt. brown                                                                           lt. brown                                     434  XLIV    168    colorless                                                                           v.lt.brown                                                                          dk. straw                                     452  XLV    --      colorless                                                                           tan   dk. straw                                     453  XLV    1076    v.lt.straw                                                                          lt. brown                                                                           dk. straw                                     454  XLV     168    colorless                                                                           lt. brown                                                                           dk. straw                                     422  XXVI   --      colorless                                                                           lt. brown                                                                           lt. brown                                     423  XXVI    168    colorless                                                                           lt. brown                                                                           lt. straw                                     427  XXXVII --      colorless                                                                           lt. straw                                                                           lt. straw                                     428  XXXVII  168    colorless                                                                           lt. straw                                                                           straw                                         __________________________________________________________________________

                  TABLE E                                                         ______________________________________                                        Comparative Heat Aging Data at 120° C.                                        Contain no Irganox 1076                                                                     Contain Irganox 1076                                     Example  Initial 1 Day   3 Day Initial                                                                             1 Day 3 Day                              No.      YID     ΔYID                                                                            ΔYID                                                                          YID   ΔYID                                                                          ΔYID                         ______________________________________                                        U.S. Pat. No.                                                                 4,824,884                                                                     VIIA     21.6    58.7    119.3 19.6  88.0  53.4                               VIIB     14.8    46.7    97.9  16.5  98.7  85.5                               XII      18.1    40.7    70.4  17.9  67.5  111.8                              IB       15.5    16.8    45.2                                                 IIIB     21.2    23.3    37.2                                                 XI       15.1    28.7    65.8  28.9  34.1  87.6                               (recrystd)                                                                    Present                                                                       Invention                                                                     XXII     25.5    5.8     9.0   18.5  1.3   11.1                               XXXIX    16.4    3.1     11.8  17.6  4.2   24.2                               XL       15.0    0.8     14.2  16.1  7.6   32.4                               XXXVI    16.9    -8.8    0.6   18.3  -6.6  -4.4                               XLI      16.2    2.1     13.6  17.8  4.3   30.7                               XXXVIII  16.4    -21.6   -21.0l                                               ______________________________________                                    

                                      TABLE F                                     __________________________________________________________________________    Comparative Heat Aging Data at 140° C.                                 Tensile                   Initial                                                                           3 Day 5 Day                                     Bar No.                                                                            Compound of                                                                              Antioxidant                                                                             YID ΔYID                                                                          ΔYID                                __________________________________________________________________________    Compounds of U.S. Pat. No. 4,824,884                                               Patent Example                                                           182  XII        none      18.7                                                                              44.5  79.5                                      183  XII        0.2% UV Chek                                                                            19.6                                                                              49.6  75.0                                      184  XII        0.1% UV Chek                                                                            20.3                                                                              51.8  58.7                                      185  XII        0.2% Cyasorb 2908                                                                       18.5                                                                              41.0  80.9                                      186  XI         none      16.3                                                                              45.7  71.1                                      187  XI         0.2% UV Chek                                                                            17.0                                                                              51.5  47.6                                      188  XI         0.1% UV Chek                                                                            17.2                                                                              53.1  43.6                                      189  XI         0.2% Cyasorb 2908                                                                       17.8                                                                              49.7  59.6                                      Compounds of the Present Invention                                                 Application Example                                                      190  III        none      24.8                                                                              3.2   9.7                                       191  III        Irganox 1076                                                                            27.6                                                                              2.9   17.1                                      192  III        0.2% UV Chek                                                                            27.2                                                                              -1.2  6.4                                       198  XVI        none      42.0                                                                              -22.1 -19.1                                     199  XVI        Irganox 1076                                                                            41.9                                                                              -18.6 -14.1                                     200  XVI        0.2% UV Chek                                                                            39.9                                                                              -20.0 -19.1                                     __________________________________________________________________________

As can be seen from the results set forth in Tables A-F, the tensilebars containing compounds of the present invention demonstratedsignificantly less discoloration than those containing the compounds ofU.S. Pat. No. 4,824,884. For example, a comparison of the resultsdemonstrated in Tables A-B versus that set forth in Tables C-D, clearlyshows that the polypropylene tensile bars containing the presentcompounds were less discolored after heat aging for periods of up to 100days. It is noted that the heat aging tests conducted on the tensilebars containing the present compounds (Tables C and D) were conducted ata temperature 5° C. lower than those conducted on the tensile barscontaining the comparative compounds (Tables A and B). However, theresulting differences in discoloration were so great that thetemperature variation is not significant.

A comparison of the results set forth in Tables E and F clearly showsthat the Yellowing Index increased much faster and to a much greaterdegree in the tensile bars containing the compound of the U.S. Pat. No.4,824,884 patent than those containing the present compounds, whetherantioxidants are present or not.

The present invention may be embodied in other specific forms withoutdeparting from the spirit or essential attributes thereof and,accordingly, reference should be made to the appended claims, ratherthan to the foregoing specification as indicating the scope of theinvention.

We claim:
 1. A compound having the formula ##STR72## wherein R ishydrogen, oxyl, hydroxy, substituted or unsubstituted aliphatic of 1-20carbons, substituted or unsubstituted alicyclic of 5-12 carbons,substituted or unsubstituted araliphatic of 7-22 carbons, substituted orunsubstituted aliphatic acyl of 2-20 carbons, substituted orunsubstituted alicyclic acyl of 7-16 carbons, substituted orunsubstituted aryl acyl of 7-11 carbons, substituted or unsubstitutedaraliphatic acyl of 8-22 carbons, --C(═O)N(R⁶)(R⁷), --C(═O))_(a) O--R⁸,--(CH₂)_(a) C(═O)O--R⁹ or --(CH₂ --CH(R¹)--O)_(b) --R¹⁰ ;n is 1 or 2; ais 1 or 2; b is an integer of 2-50; R¹ is hydrogen or lower alkyl of 1-4carbons; R² is hydrogen, substituted or unsubstituted aliphatic of 1-20carbons, substituted or unsubstituted alicyclic of 5-12 carbons,substituted or unsubstituted aryl of 6-14 carbons, substituted orunsubstituted araliphatic of 7-22 carbons, 2-cyanoethyl or a radical ofthe formula ##STR73## where R and R¹ are as previously defined; R³ is adirect bond, a substituted or unsubstituted aliphatic diradical of 1-20carbons, a substituted or unsubstituted aryl diradical of 6-12 carbons,a substituted or unsubstituted alicyclic diradical of 5-12 carbons or asubstituted or unsubstituted araliphatic diradical of 7-22 carbons,where the diradical may contain 1-6 --O--, --S-- or --NH-- heteroatomswith the proviso that multiple heteroatoms must be separated from eachother and the diradical ends by at least one carbon atom; R² and R³ maybe linked together to form a 5-membered lactam ring; R⁴ is hydrogen,substituted or unsubstituted aliphatic of 1-20 carbons, substituted orunsubstituted alicyclic of 5-12 carbons or substituted or unsubstitutedaraliphatic of 7-22 carbons; when n is 1, R⁵ is --N═C(R¹¹) (R¹²) ,--N(R¹³)(R¹⁴) or --N(R⁶)--Q--R¹⁵, when n is 2, R⁵ is --N(R⁶)--Q--R¹⁷--Q--N(R⁶)--; Q is --C(═O)--, --C(═O)--O--, --C(═O)--N(R⁴)--,--C(═S)--N(R⁴)-- or --S(═O)₂ --, in which R⁴ is as previously defined;R⁶ and R⁷ are independently hydrogen, substituted or unsubstitutedaliphatic of 1-20 carbons, substituted or unsubstituted alicyclic of5-12 carbons, substituted or unsubstituted aryl of 6-14 carbons orsubstituted or unsubstituted araliphatic of 7-22 carbons; R⁸ issubstituted or unsubstituted aliphatic of 1-20 carbons, substituted orunsubstituted alicyclic of 5-12 carbons, substituted or unsubstitutedaryl of 6-14 carbons or substituted or unsubstituted araliphatic of 7-22carbons; R⁹ is hydrogen, substituted or unsubstituted aliphatic of 1-20carbons, substituted or unsubstituted alicyclic of 5-12 carbons,substituted or unsubstituted aryl of 6-14 carbons or substituted orunsubstituted araliphatic of 7-22 carbons; R¹⁰ is hydrogen or aliphaticof 1-4 carbons; R¹¹ and R¹² are independently hydrogen, substituted orunsubstituted aliphatic of 1-20 carbons, substituted or unsubstitutedalicyclic of 5-12 carbons, substituted or unsubstituted aryl of 6-14carbons, substituted or unsubstituted araliphatic of 7-22 carbons; R¹¹and R¹² may be linked together to form a substituted or unsubstitutedalicyclic ring of 5-12 carbons or may be linked together through an--O--, --S-- or --NH-- heteroatom to form a heterocyclic ring of 5-12atoms wherein the --NH-- may be substituted by lower alkyl of 1-4carbons; R¹³ is hydrogen, substituted or unsubstitued aliphatic of 1-20carbons, substituted or unsubstituted alicyclic of 5-12 carbons,substituted or unsubstituted araliphatic of 7-22 carbons or substitutedor unsubstituted aryl of 6-14 carbons, where the R¹³ substituents arechloro, bromo, cyano, hydroxy, epoxy, alkyl of 1-20 carbons, cycloalkylof 5-12 carbons, aryl of 6-14 carbons, aralkyl of 7-22 carbons, alkoxyof 1-20 carbons, cycloalkoxy of 5-12 carbons, aryloxy of 6-14 carbons,aralkoxy of 7-15 carbons, aliphatic acyloxy of 2-20 carbons, alicyclicacyloxy of 6-13 carbons, aryl acyloxy of 7-15 carbons, alkylthio of 1-12carbons, trialkoxysilyl of 3-12 carbons or araliphatic acyloxy of 8-16carbons, wherein any alkyl or cycloalkyl substituent group may containisolated double bonds; R¹⁴ is substituted or unsubstitued aliphatic of1-20 carbons, substituted or unsubstituted allcyclic of 5-12 carbons,substituted or unsubstituted araliphatic of 7-22 carbons or substitutedor unsubstituted aryl of 6-14 carbons, where the R¹⁴ substituents arechloro, bromo, cyano, hydroxy, epoxy, alkyl of 1-20 carbons, cycloalkylof 5-12 carbons, aryl of 6-14 carbons, aralkyl of 7-22 carbons, alkoxyof 1-20 carbons, cycloalkoxy of 5-12 carbons, aryloxy of 6-14 carbons,aralkoxy of 7-15 carbons, aliphatic acyloxy of 2-20 carbons, alicyclicacyloxy of 6-13 carbons, aryl acyloxy of 7-15 carbons, alkylthio of 1-12carbons, trialkoxysilyl of 3-12 carbons or araliphatic acyloxy of 8-16carbons, wherein any alkyl or cycloalkyl substituent group may containisolated double bonds; R¹⁵ is hydrogen, substituted or unsubstitutedaliphatic of 1-20 carbons, substituted or unsubstituted alicyclic of5-12 carbons, substituted or unsubstituted aryl of 6-14 carbons orsubstituted or unsubstituted araliphatic of 7-22 carbons; when Q is--C(═O)--, R¹⁵ may also be 2-(3,5-dialkyl-4-hydroxyphenyl)ethyl of 13-21carbons, 3,5-dialkyl-4-hydroxyphenyl of 11-19 carbons in which the alkylgroups are branched or unbranched alkyl of 1-8 carbons,4-benzoyl-3-hydroxyphenoxymethyl, 2-alkylthioethyl of 3-20 carbons,alkylthiomethyl of 2-20 carbons, 2-(dialkylaminoalkylthio)ethyl of 5-30carbons or R¹⁶ --NH--C(═O)--R³ --; when Q is --C(═O)--O--, R¹⁵ may alsobe 2,2,6,6-tetramethyl-4-piperidinyl, in which the piperidinyl nitrogenis unsubstituted or substituted with methyl, ethyl, allyl, oxyl,hydroxyl, benzyl, benzoyl or acetyl;2-(3-hydroxy-4-benzoylphenoxy)ethyl; 2-acryloyloxyethyl;2-methacryloyloxyethyl; 2-(3-hydroxy-4-benzotriazol-2-ylphenoxy)ethyl;3-(3-benzotriazol-2-yl-4-hydroxyphenyl)propyl, in which thebenzotriazolyl may be substituted in the 5 position with chlorine,methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl and the phenyl groupmay be substituted ortho to the hydroxy group with an alkyl group of1-12 carbons or an aralkyl group of 9-12 carbons;2-(3,5-dialkyl-4-hydroxyphenyl)ethyl of 13-21 carbons,3-(3,5-dialkyl-4hydroxyphenyl)propyl of 14-22 carbons or2-[3-(3,5-dialkyl-4-hydroxyphenyl)propionyloxy]ethyl of 16-24 carbons,in which the alkyl groups are branched or unbranched alkyl of 1-8carbons; with the proviso that when Q is --(C═O)--O--, R¹⁵ is nothydrogen; R¹⁶ is substituted or unsubstituted aliphatic of 1-20 carbons,substituted or unsubstituted alicyclic of 5-12 carbons, substituted orunsubstituted aryl of 6-14 carbons, substituted or unsubstitutedaraliphatic of 7-22 carbons, 3,5-dialkyl-4-hydroxyphenyl of 11-19carbons in which the alkyl groups are independently branched orunbranched alkyl of 1-8 carbons or 2,2,6,6-tetramethyl-4-piperidinyl, inwhich the nitrogen may be substituted with methyl, ethyl, allyl, oxyl,hydroxyl, benzyl, benzoyl or acetyl; and R¹⁷ is a substituted orunsubstituted aliphatic diradical of 1-20 carbons, substituted orunsubstituted aryl diradical of 6-12 carbons, substituted orunsubstituted alicyclic diradical of 5-12 carbons or substituted orunsubstituted araliphatic diradical of 7-22 carbons, where thediradicals may contain 1-6 --O--, --S-- or --NH-- heteroatoms, with theproviso that multiple heteroatoms must be separated from each other andthe diradical ends by at least one carbon atom; substituents for any ofR, R², R³, R⁴, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², R¹⁵, R¹⁶ or R¹⁷ areindependently selected from the group consisting of one or more ofchloro, bromo, alkyl of 1-8 carbons, alkoxy of 1-8 carbons, phenoxy,cyano, hydroxy, epoxy, carboxy, alkoxycarbonyl of 2-6 carbons,alkanoyloxy of 1-4 carbons, alkanoyl of 1-4 carbons, acryloyl,acryloyloxy, methacryloyl, methacryloyloxy, hydroxymethyl,2-hydroxyethyl, alkylthio of 1-4 carbons or trialkoxysilyl of 3-12carbons, with the proviso that when Q is --C(═O)--, R¹⁵ may not besubstituted with a carboxy group; and where R is 2-hydroxy substitutedaliphatic or 2-hydroxy substituted allcyclic, substituents for R arealso selected from the group consisting of aliphatic of 1-20 carbons,alicyclic of 5-12 carbons, aryl of 6-14 carbons, araliphatic of 7-22carbons, alkoxy of 1-20 carbons, cycloalkoxy of 5-12 carbons, aryloxy of6-14 carbons, aralkoxy of 7-15 carbons, aliphatic acyloxy of 2-20carbons, alicyclic acyloxy of 6-13 carbons, aryl acyloxy of 7-15 carbonsor araliphatic acyloxy of 8-16 carbons, where any alkyl or cycloalkylsubstituent group of the 2-hydroxy substituted group may containisolated double bonds.
 2. The compound according to claim 1 whereinR ishydrogen, substituted or unsubstituted alkyl of 1-10 carbons,substituted or unsubstituted alkenyl of 3-8 carbons, substituted orunsubstituted benzyl of 7-9 carbons, 2-cyanoethyl, acetyl, substitutedor unsubstituted benzoyl, 2-hydroxyalkyl of 2-10 carbons,2-hydroxy-3-phenoxypropyl or 2-hydroxy-3-(2-ethylhexoxy)propyl; R¹ ishydrogen or methyl; R² is hydrogen, alkyl of 1-4 carbons or2,2,6,6-tetramethyl-4-piperidinyl; R³ is a direct bond, an alkylenediradical of 1-8 carbons or an o-, m- or p-phenylene diradical; or R²and R³ may be linked together to form a 5-membered lactam ring; R⁴ ishydrogen; when n is 1, R⁵ is --N═C(R¹¹)(R¹²) , --N(R¹³)(R¹⁴) or--N(R⁶)--Q--R¹⁵ ; Q is --C(═O)--, --C(═O)--O-- or --C(═O)--N(R⁴)--; R⁶is hydrogen, substituted or unsubstituted aliphatic of 1-18 carbons,substituted or unsubstituted phenyl or substituted or unsubstitutedbenzyl; R¹¹ and R¹² are independently hydrogen, alkyl of 1-8 carbons,cycloalkyl of 5-8 carbons, substituted or unsubstituted aryl of 6-12carbons, where the substituents are one or more of hydroxy or loweralkyl of 1-4 carbons or R¹¹ and R¹² are linked together to form analicyclic ring of 5-8 carbons or are linked together through a nitrogenatom to form a 2,2,6,6-tetramethyl-4-piperidinyl ring; R¹³ is hydrogenand R¹³ and R¹⁴ are independently alkyl of 1-10 carbons, cycloalkyl of5-8 carbons, aralkyl of 7-9 carbons, phenyl, substituted orunsubstituted 2-hydroxyalkyl of 2-12 carbons or substituted orunsubstituted 2-hydroxycycloalkyl of 5-8 carbons, where the substituentsare alkyl of 1-8 carbons, cycloalkyl of 5-8 carbons, aryl of 6-10carbons, alkoxy of 1-8 carbons, aryloxy of 6-14 carbons, aliphaticacyloxy of 2-8 carbons, cycloaliphatic acyloxy of 6-9 carbons, aromaticacyloxy of 7-10 carbons or araliphatic acyloxy of 8-10 carbons; R¹⁵ isaliphatic of 1-18 carbons, aryl of 6-12 carbons, araliphatic of 7-18carbons or alicyclic of 6-8 carbons; when Q is --C(═O)--, R¹⁵ is also3,5-di-t-alkyl-4-hydroxyphenyl of 14-18 carbons,2-(3,5-di-t-alkyl-4-hydroxyphenyl)ethyl of 16-20 carbons,4-benzoyl-3-hydroxyphenoxymethyl, 2-alkylthioethyl of 8-20 carbons orR¹⁶ --NH--C(═O)--R³ --, where R³ is a direct bond or a 1,2-ethylenediradical; when Q is --C(═O)--O--, R¹⁵ is also2,2,6,6-tetramethyl-4-piperidinyl in which the piperidinyl nitrogen isunsubstituted or substituted with methyl, benzoyl or acetyl;2-(3-hydroxy-4-benzoylphenoxy)ethyl;2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl;3-(3,5-di-t-butyl-4-hydroxyphenyl)propyl;2-(3-hydroxy-4-benzotriazol-2-ylphenoxy)ethyl; 2-acryloyloxyethyl or2-methacryloyloxyethyl; R¹⁶ is hydrogen, alkyl of 1-12 carbons, aryl of6-10 carbons, 3,5-di-t-alkyl-4-hydroxyphenyl of 14-18 carbons or2,2,6,6-tetramethyl-4-piperidinyl which may be substituted on thepiperidinyl nitrogen with methyl or acetyl; and when n is 2, R⁵ is--N(R⁶)--Q--R¹⁷ --Q--N(R⁶)--, where Q is --C(═O)--, --C(═O)--O-- or--C(═O)--N(R⁴)--; and R¹⁷ is an aliphatic diradical of 2-12 carbons, acycloalkylene diradical of 5-12 carbons, an alicyclic diradical of 7-12carbons, an aryl diradical of 6-12 carbons, an aralkylene diradical of7-12 carbons.
 3. The compound according to claim 2 whereR is hydrogen,methyl, acetyl or benzoyl; R¹ and R² are hydrogen; R³ is a direct bondor an alkylene diradical of 1-7 carbons; R⁴ is hydrogen; when n is 1, R⁵is --N═C(R¹¹)(R¹²), --N(R¹³)(R¹⁴) or --N(R⁶)--Q--R¹⁵ ; Q is --C(═O)--,--C(═O)--O-- or --C(═O)--NH--; R⁶ is hydrogen, methyl or ethyl; R¹¹ andR¹² are independently lower alkyl of 1-4 carbons or R¹¹ and R¹² arelinked together to form a cyclopentyl, cyclohexyl or cyclooctyl ring orare linked together through a nitrogen atom to form a2,2,6,6-tetramethyl-4-piperidinyl ring; R¹³ is hydrogen and R¹³ and R¹⁴are independently alkyl of 1-4 carbons, cyclohexyl, benzyl, phenyl,substituted or unsubstituted 2-hydroxyalkyl of 2-10 carbons orsubstituted or unsubstituted 2-hydroxycyclohexyl where the substituentsare alkyl of 1-8 carbons, phenoxy, acetoxy, acryloyloxy, methacryloyloxyor benzoyloxy; R15 is alkyl of 1-18 carbons, phenyl, 2-hydroxyphenyl ordimethyl-m-isopropenylbenzyl; when Q is --C(═O)--, R¹⁵ is also3,5-di-t-butyl-4-hydroxyphenyl, 2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl,4-benzoyl-3-hydroxyphenoxymethyl, undecyl, heptadecyl or R¹⁶--NH--C(═O)--R³ --; when Q is --C(═O)--O--, R¹⁵ is also allyl,methallyl, 2,2,6,6-tetramethyl-4-piperidinyl,1,2,2,6,6-pentamethyl-4-piperidinyl, or2-(3-hydroxy-4-benzoylphenoxy)ethyl; R¹⁶ is3,5-di-t-butyl-4-hydroxyphenyl or 2,2,6,6-tetramethyl-4-piperidinyl;when n is 2, R⁵ is --NH--Q--R¹⁷ --Q--NH--, where Q is --C(═O)-- or--C(═O)--NH--; and R¹⁷ is an alkylene diradical of 2-10 carbons or ano-, m- or p-phenylene diradical which may be substituted with methyl,cycloalkylene of 9-10 carbons or aralkylene of 8-12 carbons.
 4. Thecompound according to claim 3 where n is 1, R and R⁴ are hydrogen, R³ isa direct bond or a 1,2-ethylene diradical, R⁵ is --NH--C(═O)--NH--R¹⁵and R¹⁵ is methyl, ethyl, phenyl, isopropyl, n-butyl, octadecyl ordimethyl-m-isopropenylbenzyl.
 5. The compound according to claim 4 whereR³ is a direct bond and R¹⁵ is phenyl, n-butyl, octadecyl ordimethyl-m-isopropenylbenzyl.
 6. The compound according to claim 4 whereR³ is a 1,2-ethylene diradical and R¹⁵ is n-butyl.
 7. The compoundaccording to claim 3 where n is 2, R and R⁴ are hydrogen, R³ is a directbond, R⁵ is --NH--C(═O)--NH--R¹⁷ --C(═O)--NH-- and R¹⁷ is a1,6-hexamethylene, 2,4-tolylene, 1,4-phenylenebis(1-methylethyl) or1,3,3-trimethylhexahydrotoluene-alpha,5-diyl diradical.
 8. The compoundaccording to claim 3 where n is 1, R and R⁴ are hydrogen, R³ is a directbond, R⁵ is --NH--C(═O)--R¹⁵ and R¹⁵ is methyl, ethyl, propyl,isopropyl, butyl, pentyl, hexyl, heptyl, nonyl, undecyl, tridecyl,pentadecyl, heptadecyl, phenyl, 2-hydroxyphenyl,3,5-di-t-butyl-4-hydroxyphenyl, 2-(3,5-di-t-butyl-4-hydroxyphenyl)ethylor 4-benzoyl-3-hydroxyphenoxy-methyl.
 9. The compound according to claim3 where n is 1, R and R⁴ are hydrogen, R³ is a direct bond, R⁵ is--NH--C(═O)--R¹⁵ R¹⁵ is R¹⁶ --NH--C(═O)-- and R¹⁶ is3,5-di-t-butyl-4-hydroxyphenyl or 2,2,6,6-tetramethyl-4-piperidinyl. 10.The compound according to claim 3 where n is 2, R and R⁴ are hydrogen,R³ is a direct bond, R⁵ is --NH--C(═O)--R¹⁷ --C(═O)--NH-- and R¹⁷ is a1,2-ethylene, 1,4-butylene, 1,3-phenylene or 1,4-phenylene diradical.11. The compound according to claim 3 where n is 1, R and R⁴ arehydrogen, R³ is a direct bond, R⁵ is --N═C(R¹¹)(R¹²), R¹¹ and R¹² areindependently lower alkyl of 1-4 carbons or R¹¹ and R¹² are linkedtogether to form a cyclohexyl ring or are linked together through anitrogen atom to form a 2,2,6,6-tetramethyl-4-piperidinyl ring.
 12. Thecompound according to claim 11 where R¹¹ and R¹² are methyl.
 13. Thecompound according to claim 11 where R¹¹ is methyl and R¹² is ethyl. 14.The compound according to claim 11 where R¹¹ and R¹² are linked togetherto form a cyclohexyl ring.
 15. The compound according to claim 11 whereR¹¹ and R¹² are linked together through a nitrogen atom to form a2,2,6,6-tetramethyl-4-piperidinyl ring.
 16. The compound according toclaim 2 where n is 1, R, R¹, R² and R⁴ are hydrogen R³ is a direct bond,R⁵ is --N═C(R¹¹)(R¹²), R¹¹ is hydrogen and R¹² is3,5-di-t-butyl-4-hydroxyphenyl.
 17. The compound according to claim 1where n is 1, R, R¹, R² and R⁴ are hydrogen R³ is a direct bond and R⁵is --NH--S(═O)₂ --C₆ H₅.
 18. The compound according to claim 1 where nis 1, R, R¹, R² and R⁴ are hydrogen R³ is a direct bond and R⁵ is--NH--C(═S)--NH--n--C₄ H₉.
 19. The compound according to claim 3 where nis 1, R, R¹, R² and R⁴ are hydrogen R³ is a direct bond, R⁵ is--NH--C(═O)--O--R¹⁵ and R¹⁵ is methyl, ethyl, propyl, isopropyl,n-butyl, allyl or methallyl.
 20. The compound according to claim 3,where R, R¹, R² and R⁴ are hydrogen, R³ is a direct bond and R⁵ is--NH--C(═O)--C₂ H₅.
 21. The compound according to claim 2 where n is 1,R, R¹, R² and R⁴ are hydrogen, R³ is a direct bond, R⁵ is--NH--C(═O)--O--R¹⁵ and R¹⁵ is 2,2,6,6-tetramethyl-4-piperidinyl inwhich the piperidinyl nitrogen is unsubstituted or substituted withmethyl, benzoyl or acetyl; 2-(3-hydroxy-4-benzoylphenoxy) ethyl;2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl;3-(3,5-di-t-butyl-4-hydroxyphenyl)propyl;2-(3-hydroxy-4-benzotriazol-2-ylphenoxy)ethyl; 2-acryloyloxyethyl or2-methacryloyloxyethyl.
 22. The compound according to claim 21 where R¹⁵is 2,2,6,6-tetramethyl-4-piperidinyl,1,2,2,6,6-pentamethyl-4-piperidinyl, or2-(3-hydroxy-4-benzoylphenoxy)ethyl.
 23. The compound according to claim2 where n is 1, R is hydrogen or 2-hydroxy-3-phenoxypropyl, R¹, R² andR⁴ are hydrogen R³ is a direct bond, R⁵ is --N(R¹³)(R¹⁴), R¹³ ishydrogen or 2-hydroxy-3-phenoxypropyl or R¹⁴ is2-hydroxy-3-phenoxypropyl.
 24. The compound according to claim 2 where nis 1, R is hydrogen or 2-hydroxy-3-(2-ethylhexoxy)propyl, R¹, R² and R⁴are hydrogen, R³ is a direct bond, R⁵ is --N(R¹³)(R¹⁴), R¹³ is hydrogenor 2-hydroxy-3-(2-ethylhexoxy)propyl and R¹⁴ is2-hydroxy-3-(2-ethylhexoxy)propyl.
 25. The compound according to claim 8where R¹⁵ is 2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl.